Multi-Stage Device and Process for Production of a Low Sulfur Heavy Marine Fuel Oil

ABSTRACT

A multi-stage process for the production of an ISO 8217 compliant Product Heavy Marine Fuel Oil from ISO 8217 compliant Feedstock Heavy Marine Fuel Oil involving a Reaction System composed of one or more reactor vessels selected from a group reactor wherein said one or more reactor vessels contains one or more reaction sections configured to promote the transformation of the Feedstock Heavy Marine Fuel Oil to the Product Heavy Marine Fuel Oil. The Product Heavy Marine Fuel Oil has a Environmental Contaminate level has a maximum sulfur content (ISO 14596 or ISO 8754) between the range of 0.05 mass % to 1.0 mass. A process plant for conducting the process for conducting the process is disclosed that can utilize a modular reactor vessel.

This application is a continuation of co-pending U.S. application Ser.No. 17/942,906, filed 12 Sep. 2022; which is a continuation of U.S.application Ser. No. 17/199,148, filed 11 Mar. 2021, now U.S. Pat. No.11,441,084; which is a continuation/divisional application of U.S.application Ser. No. 16/681,036, filed 12 Nov. 2019, now U.S. Pat. No.10,954,456; which is a continuation/divisional application of U.S.application Ser. No. 16/103,895, filed 14 Aug. 2018, now U.S. patentSer. No. 10/563,133 issued 18 Feb. 2020; U.S. application Ser. No.16/103,895 is: a continuation-in-part of PCT/US2018/017863 filed 12 Feb.2018, which claims benefit of U.S. Provisional Application No.62/589,479, filed 21 Nov. 2017 and claims benefit of U.S. ProvisionalApplication No. 62/458,002, filed 12 Feb. 2017; and U.S. applicationSer. No. 16/103,895 is a continuation-in-part of PCT/US2018/017855 filed12 Feb. 2018, which claims benefit of U.S. Provisional Application No.62/589,479, filed 21 Nov. 2017 and claims benefit of U.S. ProvisionalApplication No. 62/458,002, filed 12 Feb. 2017, all of which areincorporated by reference.

BACKGROUND

There are two basic marine fuel types: distillate based marine fuel,also known as Marine Gas Oil (MGO) or Marine Diesel Oil (MDO); andresidual based marine fuel, also known as heavy marine fuel oil (HMFO).Distillate based marine fuel both MGO and MDO, comprises petroleummiddle distillate fractions separated from crude oil in a refinery via adistillation process. Gasoil (also known as medium diesel) is apetroleum middle distillate in boiling range and viscosity betweenkerosene (light distillate) and lubricating oil (heavy distillate)containing a mixture of C₁₀ to C₁₉ hydrocarbons. Gasoil (a heavydistillate) is used to heat homes and is used blending with lightermiddle distillates as a fuel for heavy equipment such as cranes,bulldozers, generators, bobcats, tractors and combine harvesters.Generally maximizing middle distillate recovery from heavy distillatesmixed with petroleum residues is the most economic use of thesematerials by refiners because they can crack gas oils into valuablegasoline and distillates in a fluid catalytic cracking (FCC) unit.Diesel oils for road use are very similar to gas oils with road usediesel containing predominantly contain a middle distillate mixture ofC₁₀ through C₁₉ hydrocarbons, which include approximately 64% aliphatichydrocarbons, 1-2% olefinic hydrocarbons, and 35% aromatic hydrocarbons.Distillate based marine fuels (MDO and MGO) are essentially road dieselor gas oil fractions blended with up to 15% residual process streams,and optionally up to 5% volume of polycyclic aromatic hydrocarbons(asphaltenes). The residual and asphaltene materials are blended intothe middle distillate to form MDO and MGO as a way to both swell volumeand productively use these low value materials.

Asphaltenes are large and complex polycyclic hydrocarbons with apropensity to form complex and waxy precipitates, especially in thepresence of aliphatic (paraffinic) hydrocarbons that are the primarycomponent of Marine Diesel. Once asphaltenes have precipitated out, theyare notoriously difficult to re-dissolve and are described as fuel tanksludge in the marine shipping industry and marine bunker fuelingindustry. One of skill in the art will appreciate that mixing MarineDiesel with asphaltenes and process residues is limited by thecompatibility of the materials and formation of asphaltene precipitatesand the minimum Cetane number required for such fuels.

Residual based fuels or Heavy Marine Fuel Oil (HMFO) are used by largeocean-going ships as fuel for large two stroke diesel engines for over50 years. HMFO is a blend of the residues generated throughout the crudeoil refinery process. Typical refinery streams combined to from HMFO mayinclude, but are not limited to: atmospheric tower bottoms (i.e.atmospheric residues), vacuum tower bottoms (i.e. vacuum residues)visbreaker residue, FCC Light Cycle Oil (LCO), FCC Heavy Cycle Oil (HCO)also known as FCC bottoms, FCC Slurry Oil, heavy gas oils and delayedcracker oil (DCO), deasphalted oils (DAO); heavy aromatic residues andmixtures of polycylic aromatic hydrocarbons, reclaimed land transportmotor oils; pyrolysis oils and tars; aspahltene solids and tars; andminor portions (often less than 20% vol.) of middle distillate materialssuch as cutter oil, kerosene or diesel to achieve a desired viscosity.HMFO has a higher aromatic content (especially polynuclear aromatics andasphaltenes) than the marine distillate fuels noted above. The HMFOcomponent mixture varies widely depending upon the crude slate (i.e.source of crude oil) processed by a refinery and the processes utilizedwithin that refinery to extract the most value out of a barrel of crudeoil. The HMFO is generally characterized as being highly viscous, highin sulfur and metal content (up to 5 wt %), and high in asphaltenesmaking HMFO the one product of the refining process that hashistorically had a per barrel value less than feedstock crude oil.

Industry statistics indicate that about 90% of the HMFO sold contains3.5 weight % sulfur. With an estimated total worldwide consumption ofHMFO of approximately 300 million tons per year, the annual productionof sulfur dioxide by the shipping industry is estimated to be over 21million tons per year. Emissions from HMFO burning in ships contributesignificantly to both global marine air pollution and local marine airpollution levels.

The International Convention for the Prevention of Pollution from Ships,also known as the MARPOL convention or just MARPOL, as administered bythe International Maritime Organization (IMO) was enacted to preventmarine pollution (i.e. marpol) from ships. In 1997, a new annex wasadded to the MARPOL convention; the Regulations for the Prevention ofAir Pollution from Ships—Annex VI to minimize airborne emissions fromships (SO_(x), NO_(x), ODS, VOC) and their contribution to global airpollution. A revised Annex VI with tightened emissions limits wasadopted in October 2008 and effective 1 Jul. 2010 (hereafter calledAnnex VI (revised) or simply Annex VI).

MARPOL Annex VI (revised) adopted in 2008 established a set of stringentair emissions limits for all vessel and designated Emission ControlAreas (ECAs). The ECAs under MARPOL Annex VI are: i) Baltic Sea area—asdefined in Annex I of MARPOL—SO_(x) only; ii) North Sea area—as definedin Annex V of MARPOL—SO_(x) only; iii) North American—as defined inAppendix VII of Annex VI of MARPOL—SO_(x), NO_(x) and PM; and, iv)United States Caribbean Sea area—as defined in Appendix VII of Annex VIof MARPOL—SO_(x), NO_(x) and PM.

Annex VI (revised) was codified in the United States by the Act toPrevent Pollution from Ships (APPS). Under the authority of APPS, theU.S. Environmental Protection Agency (the EPA), in consultation with theUnited States Coast Guard (USCG), promulgated regulations whichincorporate by reference the full text of Annex VI. See 40 C.F.R. §1043.100(a)(1). On Aug. 1, 2012 the maximum sulfur content of all marinefuel oils used onboard ships operating in US waters/ECA was reduced from3.5% wt. to 1.00% wt. (10,000 ppm) and on Jan. 1, 2015 the maximumsulfur content of all marine fuel oils used in the North American ECAwas lowered to 0.10% wt. (1,000 ppm). At the time of implementation, theUnited States government indicated that vessel operators must vigorouslyprepare to comply with the 0.10% wt. (1,000 ppm) US ECA marine fuel oilsulfur standard. To encourage compliance, the EPA and USCG refused toconsider the cost of compliant low sulfur fuel oil to be a valid basisfor claiming that compliant fuel oil was not available for purchase. Forover five years there has been a very strong economic incentive to meetthe marine industry demands for low sulfur HMFO, however technicallyviable solutions have not been realized and a premium price has beencommanded by refiners to supply a low sulfur HMFO compliant with AnnexVI sulfur emissions requirements in the ECA areas.

Since enactment in 2010, the global sulfur cap for HMFO outside of theECA areas was set by Annex VI at 3.50% wt. effective 1 Jan. 2012; with afurther reduction to 0.50% wt, effective 1 Jan. 2020. The global cap onsulfur content in HMFO has been the subject of much discussion in boththe marine shipping and marine fuel bunkering industry. There has beenand continues to be a very strong economic incentive to meet theinternational marine industry demands for low sulfur HMFO (i.e. HMFOwith a sulfur content less than 0.50 wt. %. Notwithstanding this globaldemand, solutions for transforming high sulfur HMFO into low sulfur HMFOhave not been realized or brought to market. There is an on-going andurgent demand for processes and methods for making a low sulfur HMFOcompliant with MARPOL Annex VI emissions requirements.

Replacement of heavy marine fuel oil with marine gas oil or marinediesel: One primary solution to the demand for low sulfur HMFO to simplyreplace high sulfur HMFO with marine gas oil (MGO) or marine diesel(MDO). The first major difficulty is the constraint in global supply ofmiddle distillate materials that make up 85-90% vol of MGO and MDO. Itis reported that the effective spare capacity to produce MGO is lessthan 100 million metric tons per year resulting in an annual shortfallin marine fuel of over 200 million metric tons per year. Refiners notonly lack the capacity to increase the production of MGO, but they haveno economic motivation because higher value and higher margins can beobtained from using middle distillate fractions for low sulfur dieselfuel for land-based transportation systems (i.e. trucks, trains, masstransit systems, heavy construction equipment, etc.).

Blending: Another primary solution is the blending of high sulfur HMFOwith lower sulfur containing fuels such as MGO or MDO low sulfur marinediesel (0.1% wt. sulfur) to achieve a Product HMFO with a sulfur contentof 0.5% wt. In a straight blending approach (based on linear blending)every 1 ton of high sulfur HSFO (3.5% sulfur) requires 7.5 tons of MGOor MDO material with 0.1% wt. S to achieve a sulfur level of 0.5% wt.HMFO. One of skill in the art of fuel blending will immediatelyunderstand that blending hurts key properties of the HMFO, specificallylubricity, fuel density, CCAI, viscosity, flash point and otherimportant physical bulk properties. Blending a mostly paraffinic-typedistillate fuel (MGO or MDO) with a HMFO having a high poly aromaticcontent often correlates with poor solubility of asphaltenes. A blendedfuel is likely to result in the precipitation of asphaltenes and/orwaxing out of highly paraffinic materials from the distillate materialforming an intractable fuel tank sludge. Fuel tank sludge causesclogging of filters and separators, transfer pumps and lines, build-upof sludge in storage tanks, sticking of fuel injection pumps, andplugged fuel nozzles. Such a risk to the primary propulsion system isnot acceptable for a ship in the open ocean.

It should further be noted that blending of HMFO with marine distillateproducts (MGO or MDO) is not economically viable. A blender will betaking a high value product (0.1% S marine gas oil (MGO) or marinediesel (MDO)) and blending it 7.5 to 1 with a low value high sulfur HMFOto create a final IMO/MARPOL compliant HMFO (i.e. 0.5% wt. S Low SulfurHeavy Marine Fuel Oil—LSHMFO) which will sell at a discount to the valueof the principle ingredient (i.e. MGO or MDO).

Processing of residual oils. For the past several decades, the focus ofrefining industry research efforts related to the processing of heavyoils (crude oils, distressed oils, or residual oils) has been onupgrading the properties of these low value refinery process oils tocreate middle distillate and lighter oils with greater value. Thechallenge has been that crude oil, distressed oil and residues containhigh levels of sulfur, nitrogen, phosphorous, metals (especiallyvanadium and nickel); asphaltenes and exhibit a propensity to formcarbon or coke on the catalyst. The sulfur and nitrogen molecules arehighly refractory and aromatically stable and difficult and expensive tocrack or remove. Vanadium and nickel porphyrins and other metal organiccompounds are responsible for catalyst contamination and corrosionproblems in the refinery. The sulfur, nitrogen, and phosphorous, must beremoved because they are well-known poisons for the precious metal(platinum and palladium) catalysts utilized in the processes downstreamof the atmospheric or vacuum distillation towers.

The difficulties treating atmospheric or vacuum residual streams hasbeen known for many years and has been the subject of considerableresearch and investigation. Numerous residue-oil conversion processeshave been developed in which the goals are same: 1) create a morevaluable, preferably middle distillate range hydrocarbons; and 2)concentrate the contaminates such as sulfur, nitrogen, phosphorous,metals and asphaltenes into a form (coke, heavy coker residue, FCCslurry oil) for removal from the refinery stream. Well known andaccepted practice in the refining industry is to increase the reactionseverity (elevated temperature and pressure) to produce hydrocarbonproducts that are lighter and more purified, increase catalyst lifetimes and remove sulfur, nitrogen, phosphorous, metals and asphaltenesfrom the refinery stream.

In summary, since the announcement of the MARPOL Annex VI standardsreducing the global levels of sulfur in HMFO, refiners of crude oil havehad modest success in their technical efforts to create a process forthe production of a low sulfur substitute for high sulfur HMFO. Despitethe strong governmental and economic incentives and needs of theinternational marine shipping industry, refiners have little economicreason to address the removal of environmental contaminates from highsulfur HMFOs. The global refining industry has been focused upongenerating greater value from each barrel of oil by creating middledistillate hydrocarbons (i.e. diesel) and concentrating theenvironmental contaminates into increasingly lower value streams (i.e.residues) and products (petroleum coke, HMFO). Shipping companies havefocused on short term solutions, such as the installation of scrubbingunits, or adopting the limited use of more expensive low sulfur marinediesel and marine gas oils as a substitute for HMFO. On the open seas,most if not all major shipping companies continue to utilize the mosteconomically viable fuel, that is HMFO. There remains a long standingand unmet need for processes and devices that remove the environmentalcontaminants (i.e. sulfur, nitrogen, phosphorous, metals especiallyvanadium and nickel) from HMFO without altering the qualities andproperties that make HMFO the most economic and practical means ofpowering ocean going vessels.

SUMMARY

It is a general objective to reduce the environmental contaminates froma Heavy Marine Fuel Oil (HMFO) in a multi stage device implementing acore process that minimizes the changes in the desirable properties ofthe HMFO and minimizes the production of by-product hydrocarbons (i.e.light hydrocarbons having C₁-C₄ and wild naphtha (C₄-C₂₀)).

A first aspect and illustrative embodiment encompasses a multi-stagedevice for the production of a Heavy Marine Fuel Oil, the devicecomprising: means for mixing a quantity of Feedstock Heavy Marine FuelOil with a quantity of Activating Gas mixture to give a FeedstockMixture; means for heating the Feedstock mixture, wherein the means formixing and means for heating communicate with each other; a ReactionSystem in fluid communication with the means for heating, wherein theReaction System comprises one or more reactor vessels selected from thegroup consisting of: dense packed fixed bed trickle reactor; densepacked fixed bed up-flow reactor; ebulliated bed three phase up-flowreactor; fixed bed divided wall reactor; fixed bed three phase bubblereactor; fixed bed liquid full reactor, fixed bed high flux reactor;fixed bed structured catalyst bed reactor; fixed bed reactivedistillation reactor and combinations thereof, and wherein said one ormore reactor vessels contains one or more reaction sections configuredto promote the transformation of the Feedstock Mixture to a ProcessMixture; means for receiving said Process Mixture and separating theliquid components of the Process Mixture from the bulk gaseouscomponents of the Process Mixture, said means for receiving in fluidcommunication with the reaction System; and means for separating anyresidual gaseous components and by-product hydrocarbon components fromthe Process Mixture to form a Product Heavy Marine Fuel Oil. In apreferred embodiment, the Reaction System comprises two or more reactorvessel wherein the reactor vessels are configured in a matrix of atleast 2 reactors by 2 reactors. Another alternative and preferredembodiment of the Reactor System comprises at least six reactor vesselswherein the reactor vessels are configured in a matrix of at least 3reactors arranged in series to form two reactor trains and wherein the 2reactor trains arranged in parallel and configured so Process Mixturecan be distributed across the matrix.

A second aspect and illustrative embodiment encompasses a modularreactor comprising a reaction vessel's exterior shell defines aninterior space; one or more inlet piping connections to provide fluidcommunication between a source of feedstock and the interior space ofreaction vessel; one or more outlet piping connections to provide fluidcommunication between the interior of the reaction vessel and productremoval piping; a supporting framework surrounding the reaction vessel,the supporting frame work providing the reaction vessel with structuralsupport, and wherein the supporting framework is truck mountable; andone or more internal structures within the interior space of thereaction vessel. The internal structures are selected from the groupconsisting of: trays, perforated support plates, catalyst beds,structured catalyst beds, Raschig rings, Dixon rings, absorbentmaterials and combinations of these. The supporting framework may bedimensioned to conform with the size of an ISO 40 container or ISO 20foot container making the modular reactor transportable by truck orrail. The reaction vessel configurations are selected from the groupconsisting of: dense packed fixed bed trickle reactor; dense packedfixed bed up-flow reactor; ebulliated bed three phase up-flow reactor;fixed bed divided wall reactor; fixed bed three phase bubble reactor;fixed bed liquid full reactor, fixed bed high flux reactor; fixed bedstructured catalyst bed reactor; fixed bed reactive distillation reactorand combinations thereof.

A third aspect and illustrative embodiment encompasses a multi-stageprocess for the production of a Heavy Marine Fuel Oil, the processcomprising: mixing a quantity of Feedstock Heavy Marine Fuel Oil with aquantity of Activating Gas mixture to give a Feedstock Mixture;contacting the Feedstock Mixture with one or more catalysts underreactive conditions in a Reaction System to form a Process Mixture fromthe Feedstock Mixture; receiving said Process Mixture and separating theliquid components of the Process Mixture from the bulk gaseouscomponents of the Process Mixture; subsequently separating any residualgaseous components and by-product hydrocarbon components from theProduct Heavy Marine Fuel Oil; and, discharging the Product Heavy MarineFuel Oil. The Reaction System comprises one or more reactor vesselswherein the reactor vessels are selected from the group consisting of:dense packed fixed bed trickle reactor; dense packed fixed bed up-flowreactor; ebulliated bed three phase up-flow reactor; fixed bed dividedwall reactor; fixed bed three phase bubble reactor; fixed bed liquidfull reactor, fixed bed high flux reactor; fixed bed structured catalystbed reactor; fixed bed reactive distillation reactor and combinationsthereof.

DESCRIPTION OF DRAWINGS

FIG. 1 is a process block flow diagram of an illustrative core processto produce Product HMFO.

FIG. 2 is a process flow diagram of a multistage process fortransforming the Feedstock HMFO and a subsequent core process to produceProduct HMFO.

FIG. 3 is a process flow diagram of a first alternative configurationfor the Reactor System (11) in FIG. 2 .

FIG. 4 is a process flow diagram of a second alternative

FIG. 5 is a process flow diagram of as multi-reactor matrixconfiguration for the Reactor System (11) in FIG. 2 .

FIG. 6 is a process flow diagram of as multi-reactor matrixconfiguration for the Reactor System (11) in FIG. 2 .

FIG. 7 illustrates the exterior of a modular reaction vessel useful inthe multistage process for transforming Feedstock HMFO to Product HMFO.

FIG. 8 is a side view of a first illustrative embodiment of a catalystretention structure.

FIG. 9 is a side view of a first illustrative embodiment of a structuredcatalyst bed with a plurality of catalyst retention structures.

FIG. 10 is a side view of a second illustrative embodiment of a catalystretention structure.

FIG. 11 is a side view of a second illustrative embodiment of astructured catalyst bed with a plurality of catalyst retentionstructures.

FIG. 12 is a schematic illustration of a reaction vessel configured tooperate under reactive distillation conditions.

FIG. 13 is a schematic illustration of a reaction vessel configured tooperate under three phase bubble reactor conditions.

FIG. 14 is a schematic illustration of a reaction vessel configured tooperate as a divide wall fixed bed reactor conditions.

DETAILED DESCRIPTION

The inventive concepts as described herein utilize terms that should bewell known to one of skill in the art, however certain terms areutilized having a specific intended meaning and these terms are definedbelow:

Heavy Marine Fuel Oil (HMFO) is a petroleum product fuel compliant withthe ISO 8217 (2017) standards for residual marine fuels except for theconcentration levels of the Environmental Contaminates.

Environmental Contaminates are organic and inorganic components of HMFOthat result in the formation of SO_(x), NO_(x) and particulate materialsupon combustion.

Feedstock HMFO is a petroleum product fuel compliant with the ISO 8217(2017) standards for the physical properties or characteristics of amerchantable HMFO except for the concentration of EnvironmentalContaminates, more specifically the Feedstock HMFO has a sulfur contentgreater than the global MARPOL Annex VI standard of 0.5% wt. sulfur, andpreferably and has a sulfur content (ISO 14596 or ISO 8754) between therange of 5.0% wt. to 1.0% wt.

Product HMFO is a petroleum product fuel compliant with the ISO 8217(2017) standards for the physical properties or characteristics of amerchantable HMFO and has a sulfur content lower than the global MARPOLAnnex VI standard of 0.5% wt. sulfur (ISO 14596 or ISO 8754), andpreferably a maximum sulfur content (ISO 14596 or ISO 8754) between therange of 0.05% wt. to 1.0% wt.

Activating Gas: is a mixture of gases utilized in the process combinedwith the catalyst to remove the environmental contaminates from theFeedstock HMFO.

Fluid communication: is the capability to transfer fluids (eitherliquid, gas or combinations thereof, which might have suspended solids)from a first vessel or location to a second vessel or location, this mayencompass connections made by pipes (also called a line), spools,valves, intermediate holding tanks or surge tanks (also called a drum).

Merchantable quality: is a level of quality for a residual marine fueloil so the fuel is fit for the ordinary purpose it should serve (i.e.serve as a residual fuel source for a marine ship) and can becommercially sold as and is fungible and compatible with other heavy orresidual marine bunker fuels.

Bbl or bbl: is a standard volumetric measure for oil; 1 bbl=0.1589873m³; or 1bbl=158.9873 liters; or 1 bbl=42.00 US liquid gallons.

Bpd or bpd: is an abbreviation for Bbl per day.

SCF: is an abbreviation for standard cubic foot of a gas; a standardcubic foot (at 14.73 psi and 60° F.) equals 0.0283058557 standard cubicmeters (at 101.325 kPa and 15° C.).

Bulk Properties: are broadly defined as the physical properties orcharacteristics of a merchantable HMFO as required by ISO 8217 (2017);and the measurements include: kinematic viscosity at 50° C. asdetermined by ISO 3104; density at 15° C. as determined by ISO 3675;CCAI value as determined by ISO 8217, ANNEX B; flash point as determinedby ISO 2719; total sediment—aged as determined by ISO 10307-2; carbonresidue—micro method as determined by ISO 10370; and aluminum plussilicon content as determined by ISO 10478.

The inventive concepts are illustrated in more detail in thisdescription referring to the drawings, in which FIG. 1 shows thegeneralized block process flows for a core process of reducing theenvironmental contaminates in a Feedstock HMFO and producing a ProductHMFO. A predetermined volume of Feedstock HMFO (2) is mixed with apredetermined quantity of Activating Gas (4) to give a FeedstockMixture. The Feedstock HMFO utilized generally complies with the bulkphysical and certain key chemical properties for a residual marine fueloil otherwise compliant with ISO 8217 (2017) exclusive of theEnvironmental Contaminates. More particularly, when the EnvironmentalContaminate is sulfur, the concentration of sulfur in the Feedstock HMFOmay be between the range of 5.0% wt. to 1.0% wt. The Feedstock HMFOshould have bulk physical properties required of an ISO 8217 (2017)compliant HMFO. The Feedstock HMFO should exhibit the Bulk Propertiesof: a maximum of kinematic viscosity at 50° C. (ISO 3104) between therange from 180 mm²/s to 700 mm²/s; a maximum of density at 15° C. (ISO3675) between the range of 991.0 kg/m³ to 1010.0 kg/m³; a CCAI in therange of 780 to 870; and a flash point (ISO 2719) no lower than 60° C.Properties of the Feedstock HMFO connected to the formation ofparticulate material (PM) include: a total sediment—aged (ISO 10307-2)less than 0.10% wt. and a carbon residue—micro method (ISO 10370) lessthan 20.00% wt. and a aluminum plus silicon (ISO 10478) content of lessthan 60 mg/kg. Environmental Contaminates other than sulfur that may bepresent in the Feedstock HMFO over the ISO requirements may includevanadium, nickel, iron, aluminum and silicon substantially reduced bythe process of the present invention. However, one of skill in the artwill appreciate that the vanadium content serves as a general indicatorof these other Environmental Contaminates. In one preferred embodimentthe vanadium content is ISO compliant so the Feedstock HMFO has amaximum vanadium content (ISO 14597) between the range from 350 mg/kg to450 ppm mg/kg.

As for the properties of the Activating Gas, the Activating Gas shouldbe selected from mixtures of nitrogen, hydrogen, carbon dioxide, gaseouswater, and methane. The mixture of gases within the Activating Gasshould have an ideal gas partial pressure of hydrogen (p_(H2)) greaterthan 80% of the total pressure of the Activating Gas mixture (P) andmore preferably wherein the Activating Gas has an ideal gas partialpressure of hydrogen (p_(H2)) greater than 90% of the total pressure ofthe Activating Gas mixture (P). It will be appreciated by one of skillin the art that the molar content of the Activating Gas is anothercriterion the Activating Gas should have a hydrogen mole fraction in therange between 80% and 100% of the total moles of Activating Gas mixture.

The Feedstock Mixture (i.e. mixture of Feedstock HMFO and ActivatingGas) is brought up to the process conditions of temperature and pressureand introduced into a Reactor System, preferably a reactor vessel, sothe Feedstock Mixture is then contacted under reactive conditions withone or more catalysts (8) to form a Process Mixture from the FeedstockMixture.

The core process conditions are selected so the ratio of the quantity ofthe Activating Gas to the quantity of Feedstock HMFO is 250 scf gas/bblof Feedstock HMFO to 10,000 scf gas/bbl of Feedstock HMFO; andpreferably between 2000 scf gas/bbl of Feedstock HMFO 1 to 5000 scfgas/bbl of Feedstock HMFO more preferably between 2500 scf gas/bbl ofFeedstock HMFO to 4500 scf gas/bbl of Feedstock HMFO. The processconditions are selected so the total pressure in the first vessel isbetween of 250 psig and 3000 psig; preferably between 1000 psig and 2500psig, and more preferably between 1500 psig and 2200 psig. The processreactive conditions are selected so the indicated temperature within thefirst vessel is between of 500° F. to 900° F., preferably between 650°F. and 850° F. and more preferably between 680° F. and 800° F. Theprocess conditions are selected so the liquid hourly space velocitywithin the first vessel is between 0.05 oil/hour/m³ catalyst and 1.0oil/hour/m³ catalyst; preferably between 0.08 oil/hour/m³ catalyst and0.5 oil/hour/m³ catalyst; and more preferably between 0.1 oil/hour/m³catalyst and 0.3 oil/hour/m³ catalyst to achieve deep desulfurizationwith product sulfur levels below 0.1 ppmw.

One of skill in the art will appreciate that the core process reactiveconditions are determined considering the hydraulic capacity of theunit. Exemplary hydraulic capacity for the treatment unit may be between100 bbl of Feedstock HMFO/day and 100,000 bbl of Feedstock HMFO/day,preferably between 1000 bbl of Feedstock HMFO/day and 60,000 bbl ofFeedstock HMFO/day, more preferably between 5,000 bbl of FeedstockHMFO/day and 45,000 bbl of Feedstock HMFO/day, and even more preferablybetween 10,000 bbl of Feedstock HMFO/day and 30,000 bbl of FeedstockHMFO/day.

One of skill in the art will appreciate that a fixed bed reactor using asupported transition metal heterogeneous catalyst will be thetechnically easiest to implement and is preferred. However, alternativereactor types may be utilized including, but not limited to: ebullatedor fluidized bed reactors; structured bed reactors; three-phase bubblereactors; reactive distillation bed reactors and the like all of whichmay be co-current or counter current. We also assume high flux or liquidfull type reactors may be used such as those disclosed in U.S. Pat. Nos.6,123,835; 6,428,686; 6,881,326; 7,291,257; 7,569,136 and other similarand related patents and patent applications.

The transition metal heterogeneous catalyst utilized comprises a porousinorganic oxide catalyst carrier and a transition metal catalytic metal.The porous inorganic oxide catalyst carrier is at least one carrierselected from the group consisting of alumina, alumina/boria carrier, acarrier containing metal-containing aluminosilicate, alumina/phosphoruscarrier, alumina/alkaline earth metal compound carrier, alumina/titaniacarrier and alumina/zirconia carrier. The transition metal catalyticmetal component of the catalyst is one or more metals selected from thegroup consisting of group 6, 8, 9 and 10 of the Periodic Table. In apreferred and illustrative embodiment, the transition metalheterogeneous catalyst is a porous inorganic oxide catalyst carrier anda transition metal catalyst, in which the preferred porous inorganicoxide catalyst carrier is alumina and the preferred transition metalcatalyst is Ni—Mo, Co—Mo, Ni—W or Ni—Co—Mo. The process by which thetransition metal heterogeneous catalyst is manufactured is known in theliterature and preferably the catalysts are commercially available ashydrodemetallization catalysts, transition catalysts, desulfurizationcatalyst and combinations of these which might be pre-sulfided.

The Process Mixture (10) in this core process is removed from theReactor System (8) and from being in contact with the one or morecatalyst and is sent via fluid communication to a second vessel (12),preferably a gas-liquid separator or hot separators and cold separators,for separating the liquid components (14) of the Process Mixture fromthe bulk gaseous components (16) of the Process Mixture. The gaseouscomponents (16) are treated beyond the battery limits of the immediateprocess. Such gaseous components may include a mixture of Activating Gascomponents and lighter hydrocarbons (mostly methane, ethane and propanebut some wild naphtha) that may have been formed as part of theby-product hydrocarbons from the process.

The Liquid Components (16) in this core process are sent via fluidcommunication to a third vessel (18), preferably a fuel oil productstripper system, for separating any residual gaseous components (20) andby-product hydrocarbon components (22) from the Product HMFO (24). Theresidual gaseous components (20) may be a mixture of gases selected fromthe group consisting of: nitrogen, hydrogen, carbon dioxide, hydrogensulfide, gaseous water, C₁-C₅ hydrocarbons. This residual gas is treatedoutside of the battery limits of the immediate process, combined withother gaseous components (16) removed from the Process Mixture (10) inthe second vessel (12). The liquid by-product hydrocarbon component,which are condensable hydrocarbons formed in the process (22) may be amixture selected from the group consisting of C₄-C₂₀ hydrocarbons (wildnaphtha) (naphtha—diesel) and other condensable light liquid (C₃-C₅)hydrocarbons that can be utilized as part of the motor fuel blendingpool or sold as gasoline and diesel blending components on the openmarket. These liquid by-product hydrocarbons should be less than 15%wt., preferably less than 5% wt. and more preferably less than 3% wt. ofthe overall process mass balance.

The Product HMFO (24) resulting from the core process is discharged viafluid communication into storage tanks beyond the battery limits of theimmediate process. The Product HMFO complies with ISO 8217 (2017) andhas a maximum sulfur content (ISO 14596 or ISO 8754) between the rangeof 0.05 mass % to 1.0 mass % preferably a sulfur content (ISO 14596 orISO 8754) between the range of 0.05 mass % ppm and 0.7 mass % and morepreferably a sulfur content (ISO 14596 or ISO 8754) between the range of0.1 mass % and 0.5 mass %. The vanadium content of the Product HMFO isalso ISO compliant with a maximum vanadium content (ISO 14597) betweenthe range from 350 mg/kg to 450 ppm mg/kg, preferably a vanadium content(ISO 14597) between the range of 200 mg/kg and 300 mg/kg and morepreferably a vanadium content (ISO 14597) between the range of 50 mg/kgand 100 mg/kg.

The Product HFMO should have bulk physical properties that are ISO 8217(2017) compliant. The Product HMFO should exhibit Bulk Properties of: amaximum of kinematic viscosity at 50° C. (ISO 3104) between the rangefrom 180 mm²/s to 700 mm²/s; a maximum of density at 15° C. (ISO 3675)between the range of 991.0 kg/m³ to 1010.0 kg/m³; a CCAI value in therange of 780 to 870; a flash point (ISO 2719) no lower than 60.0° C.; atotal sediment—aged (ISO 10307-2) of less than 0.10 mass %; a carbonresidue—micro method (ISO 10370) lower than 20.00 mass %, and analuminum plus silicon (ISO 10478) content of less than 60 mg/kg.

Relative the Feedstock HMFO, the Product HMFO will have a sulfur content(ISO 14596 or ISO 8754) between 1% and 20% of the maximum sulfur contentof the Feedstock HMFO. That is the sulfur content of the Product will bereduced by about 80% or greater when compared to the Feedstock HMFO.Similarly, the vanadium content (ISO 14597) of the Product HMFO isbetween 1% and 20% of the maximum vanadium content of the FeedstockHMFO. One of skill in the art will appreciate that the above dataindicates a substantial reduction in sulfur and vanadium contentindicate a process having achieved a substantial reduction in theEnvironmental Contaminates from the Feedstock HMFO while maintaining thedesirable properties of an ISO 8217 compliant and merchantable HMFO.

As a side note, the residual gaseous component is a mixture of gasesselected from the group consisting of: nitrogen, hydrogen, carbondioxide, hydrogen sulfide, gaseous water, C₁-C₅ hydrocarbons. An aminescrubber will effectively remove the hydrogen sulfide content which canthen be processed using technologies and processes well known to one ofskill in the art. In one preferable illustrative embodiment, thehydrogen sulfide is converted into elemental sulfur using the well-knownClaus process. An alternative embodiment utilizes a proprietary processfor conversion of the Hydrogen sulfide to hydrosulfuric acid. Eitherway, the sulfur is removed from entering the environment prior tocombusting the HMFO in a ships engine. The cleaned gas can be vented,flared or more preferably recycled back for use as Activating Gas.

Product HMFO The Product HFMO resulting from the disclosed illustrativeprocess is of merchantable quality for sale and use as a heavy marinefuel oil (also known as a residual marine fuel oil or heavy bunker fuel)and exhibits the bulk physical properties required for the Product HMFOto be an ISO compliant (i.e. ISO 8217 (2017)) residual marine fuel oil.The Product HMFO should exhibit the Bulk Properties of: a maximum ofkinematic viscosity at 50° C. (ISO 3104) between the range from 180mm²/s to 700 mm²/s; a density at 15° C. (ISO 3675) between the range of991.0 kg/m³ to 1010.0 kg/m³; a CCAI is in the range of 780 to 870; aflash point (ISO 2719) no lower than 60° C.; a total sediment—aged (ISO10307-2) less than 0.10% wt.; a carbon residue—micro method (ISO 10370)less than 20.00% wt.; and an aluminum plus silicon (ISO 10478) contentno more than of 60 mg/kg.

The Product HMFO has a sulfur content (ISO 14596 or ISO 8754) less than0.5 wt % and preferably less than 0.1% wt. and complies with the IMOAnnex VI (revised) requirements for a low sulfur and preferably anultra-low sulfur HMFO. That is the sulfur content of the Product HMFOhas been reduced by about 80% and preferably 90% or greater whencompared to the Feedstock HMFO. Similarly, the vanadium content (ISO14597) of the Product Heavy Marine Fuel Oil is less than 20% and morepreferably less than 10% of the maximum vanadium content of theFeedstock Heavy Marine Fuel Oil. One of skill in the art will appreciatethat a substantial reduction in sulfur and vanadium content of theFeedstock HMFO indicates a process having achieved a substantialreduction in the Environmental Contaminates from the Feedstock HMFO; ofequal importance is this has been achieved while maintaining thedesirable properties of an ISO 8217 (2017) compliant HMFO.

The Product HMFO not only complies with ISO 8217 (2017) (and ismerchantable as a residual marine fuel oil or bunker fuel), the ProductHMFO has a maximum sulfur content (ISO 14596 or ISO 8754) between therange of 0.05% wt. to 1.0% wt. preferably a sulfur content (ISO 14596 orISO 8754) between the range of 0.05% wt. ppm and 0.5% wt. and morepreferably a sulfur content (ISO 14596 or ISO 8754) between the range of0.1% wt. and 0.5% wt. The vanadium content of the Product HMFO is wellwithin the maximum vanadium content (ISO 14597) required for an ISO 8217(2017) residual marine fuel oil exhibiting a vanadium content lower than450 ppm mg/kg, preferably a vanadium content (ISO 14597) lower than 300mg/kg and more preferably a vanadium content (ISO 14597) less than 50mg/kg.

One knowledgeable in the art of marine fuel blending, bunker fuelformulations and the fuel requirements for marine shipping fuels willreadily appreciate that without further compositional changes orblending, the Product HMFO can be sold and used as a low sulfur MARPOLAnnex VI compliant heavy (residual) marine fuel oil that is a directsubstitute for the high sulfur heavy (residual) marine fuel oil or heavybunker fuel currently in use. One illustrative embodiment is an ISO 8217(2017) compliant low sulfur heavy marine fuel oil comprising (andpreferably consisting essentially of) hydroprocessed ISO 8217 (2017)compliant high sulfur heavy marine fuel oil, wherein the sulfur levelsof the hydroprocessed ISO 8217 (2017) compliant high sulfur heavy marinefuel oil is greater than 0.5% wt. and wherein the sulfur levels of theISO 8217 (2017) compliant low sulfur heavy marine fuel oil is less than0.5% wt. Another illustrative embodiment is an ISO 8217 (2017) compliantultra-low sulfur heavy marine fuel oil comprising (and preferablyconsisting essentially of) a hydroprocessed ISO 8217 (2017) complianthigh sulfur heavy marine fuel oil, wherein the sulfur levels of thehydroprocessed ISO 8217 (2017) compliant high sulfur heavy marine fueloil is greater than 0.5% wt. and wherein the sulfur levels of the ISO8217 (2017) compliant low sulfur heavy marine fuel oil is less than 0.1%wt.

Because of the present invention, multiple economic and logisticalbenefits to the bunkering and marine shipping industries can berealized. The benefits include minimal changes to the existing heavymarine fuel bunkering infrastructure (storage and transferring systems);minimal changes to shipboard systems are needed to comply with emissionsrequirements of MARPOL Annex VI (revised); no additional training orcertifications for crew members will be needed, amongst the realizablebenefits. Refiners will also realize multiple economic and logisticalbenefits, including: no need to alter or rebalance the refineryoperations, crude sources, and product streams to meet a new marketdemand for low sulfur or ultralow sulfur HMFO; no additional units areneeded in the refinery with additional hydrogen or sulfur capacitybecause the illustrative process can be conducted as a stand-alone unit;refinery operations can remain focused on those products that create thegreatest value from the crude oil received (i.e. production ofpetrochemicals, gasoline and distillate (diesel); refiners can continueusing the existing slates of crude oils without having to switch tosweeter or lighter crudes to meet the environmental requirements forHMFO products.

Heavy Marine Fuel Composition One aspect of the present inventiveconcept is a fuel composition comprising, but preferably consistingessentially of, the Product HMFO resulting from the processes disclosed,and may optionally include Diluent Materials. The Product HMFO itselfcomplies with ISO 8217 (2017) and meets the global IMO Annex VIrequirements for maximum sulfur content (ISO 14596 or ISO 8754). Ifultra-low levels of sulfur are desired, the process of the presentinvention achieves this and one of skill in the art of marine fuelblending will appreciate that a low sulfur or ultra-low sulfur ProductHMFO can be utilized as a primary blending stock to form a global IMOAnnex VI compliant low sulfur Heavy Marine Fuel Composition. Such a lowsulfur Heavy Marine Fuel Composition will comprise (and preferablyconsist essentially of): a) the Product HMFO and b) Diluent Materials.In one embodiment, the majority of the volume of the Heavy Marine FuelComposition is the Product HMFO with the balance of materials beingDiluent Materials. Preferably, the Heavy Maine Fuel Composition is atleast 75% by volume, preferably at least 80% by volume, more preferablyat least 90% by volume, and furthermore preferably at least 95% byvolume Product HMFO with the balance being Diluent Materials.

Diluent Materials may be hydrocarbon or non-hydrocarbon based materialsmixed into or combined with or added to, or solid particle materialssuspended in, the Product HMFO. The Diluent Materials may intentionallyor unintentionally alter the composition of the Product HMFO but not sothe resulting mixture violates the ISO 8217 (2017) standards forresidual marine fuels or fails to have a sulfur content lower than theglobal MARPOL standard of 0.5% wt. sulfur (ISO 14596 or ISO 8754).Examples of Diluent Materials considered hydrocarbon based materialsinclude: Feedstock HMFO (i.e. high sulfur HMFO); distillate based fuelssuch as road diesel, gas oil, MGO or MDO; cutter oil (which is used informulating residual marine fuel oils); renewable oils and fuels such asbiodiesel, methanol, ethanol, and the like; synthetic hydrocarbons andoils based on gas to liquids technology such as Fischer-Tropsch derivedoils, synthetic oils such as those based on polyethylene, polypropylene,dimer, trimer and poly butylene; refinery residues or other hydrocarbonoils such as atmospheric residue, vacuum residue, fluid catalyticcracker (FCC) slurry oil, FCC cycle oil, pyrolysis gasoil, cracked lightgas oil (CLGO), cracked heavy gas oil (CHGO), light cycle oil (LCO),heavy cycle oil (HCO), thermally cracked residue, coker heavydistillate, bitumen, de-asphalted heavy oil, visbreaker residue, slopoils, asphaltinic oils; used or recycled motor oils; lube oil aromaticextracts and crude oils such as heavy crude oil, distressed crude oilsand similar materials that might otherwise be sent to a hydrocracker ordiverted into the blending pool for a prior art high sulfur heavy(residual) marine fuel oil. Examples of Diluent Materials considerednon-hydrocarbon based materials include: residual water (i.e. waterabsorbed from the humidity in the air or water that is miscible orsolubilized, sometimes as microemulsions, into the hydrocarbons of theProduct HMFO), fuel additives which can include, but are not limited todetergents, viscosity modifiers, pour point depressants, lubricitymodifiers, de-hazers (e.g. alkoxylated phenol formaldehyde polymers),antifoaming agents (e.g. polyether modified polysiloxanes); ignitionimprovers; anti rust agents (e.g. succinic acid ester derivatives);corrosion inhibitors; anti-wear additives, anti-oxidants (e.g. phenoliccompounds and derivatives), coating agents and surface modifiers, metaldeactivators, static dissipating agents, ionic and nonionic surfactants,stabilizers, cosmetic colorants and odorants and mixtures of these. Athird group of Diluent Materials may include suspended solids or fineparticulate materials that are present because of the handling, storageand transport of the Product HMFO or the Heavy Marine Fuel Composition,including but not limited to: carbon or hydrocarbon solids (e.g. coke,graphitic solids, or micro-agglomerated asphaltenes), iron rust andother oxidative corrosion solids, fine bulk metal particles, paint orsurface coating particles, plastic or polymeric or elastomer or rubberparticles (e.g. resulting from the degradation of gaskets, valve parts,etc. . . . ), catalyst fines, ceramic or mineral particles, sand, clay,and other earthen particles, bacteria and other biologically generatedsolids, and mixtures of these that may be present as suspendedparticles, but otherwise don't detract from the merchantable quality ofthe Heavy Marine Fuel Composition as an ISO 8217 (2017) compliant heavy(residual) marine fuel.

The blend of Product HMFO and Diluent Materials must be of merchantablequality as a low sulfur heavy (residual) marine fuel. That is the blendmust be suitable for the intended use as heavy marine bunker fuel andgenerally be fungible and compatible as a bunker fuel for ocean goingships. Preferably the Heavy Marine Fuel Composition must retain the bulkphysical properties required of an ISO 8217 (2017) compliant residualmarine fuel oil and a sulfur content lower than the global MARPOLstandard of 0.5% wt. sulfur (ISO 14596 or ISO 8754) so that the materialqualifies as MARPOL Annex VI Low Sulfur Heavy Marine Fuel Oil (LS-HMFO).The sulfur content of the Product HMFO can be lower than 0.5% wt. (i.e.below 0.1% wt sulfur (ISO 14596 or ISO 8754)) to qualify as a MARPOLAnnex VI compliant Ultra-Low Sulfur Heavy Marine Fuel Oil (ULS-HMFO) anda Heavy Marine Fuel Composition likewise can be formulated to qualify asa MARPOL Annex VI compliant ULS-HMFO suitable for use as marine bunkerfuel in the ECA zones. To qualify as an ISO 8217 (2017) qualified fuel,the Heavy Marine Fuel Composition of the present invention must meetthose internationally accepted standards. Those include Bulk Propertiesof: a maximum of kinematic viscosity at 50° C. (ISO 3104) between therange from 180 mm²/s to 700 mm²/s; a density at 15° C. (ISO 3675)between the range of 991.0 kg/m³ to 1010.0 kg/m³; a CCAI is in the rangeof 780 to 870; a flash point (ISO 2719) no lower than 60° C.; a totalsediment—aged (ISO 10307-2) less than 0.10% wt.; a carbon residue—micromethod (ISO 10370) less than 20.00% wt., and an aluminum plus silicon(ISO 10478) content no more than of 60 mg/kg.

Production Plant Description Production Plant Description: Turning nowto a more detailed illustrative embodiment of a production plant, FIG. 2shows a schematic for a production plant implementing the processdescribed above for reducing the environmental contaminates in aFeedstock HMFO to produce a Product HMFO according to the secondillustrative embodiment. One of skill in the art will appreciate thatFIG. 2 is a generalized schematic drawing, and the exact layout andconfiguration of a plant will depend upon factors such as location,production capacity, environmental conditions (i.e. wind load, etc.) andother factors and elements that a skilled detailed engineering firm canprovide. Such variations are contemplated and within the scope of thepresent disclosure.

In FIG. 2 , Feedstock HMFO (A) is fed from outside the battery limits(OSBL) to the Oil Feed Surge Drum (1) that receives feed from outsidethe battery limits (OSBL) and provides surge volume adequate to ensuresmooth operation of the unit. Water entrained in the feed and bulksolids (sand, rust particles, etc.) are removed from the HMFO with thewater and bulk solids being discharged a stream (1 c) for treatmentOSBL.

The Feedstock HMFO (A) is withdrawn from the Oil Feed Surge Drum (1) vialine (1 b) by the Oil Feed Pump (3) and is pressurized to a pressurerequired for the process. The pressurized HMFO (A′) then passes throughline (3 a) to the Oil Feed/Product Heat Exchanger (5) where thepressurized HMFO Feed (A′) is partially heated by the Product HMFO (B).The pressurized Feedstock HMFO (A′) passing through line (5 a) isfurther heated against the effluent from the Reactor System (E) in theReactor Feed/Effluent Heat Exchanger (7).

The heated and pressurized Feedstock HMFO (A″) in line (7 a) is thenmixed with Activating Gas (C) provided via line (23 c) at Mixing Point(X) to form a Feedstock Mixture (D). The mixing point (X) can be anywell know gas/liquid mixing system or entrainment mechanism well knownto one skilled in the art.

The Feedstock Mixture (D) passes through line (9 a) to the Reactor FeedFurnace (9) where the Feedstock Mixture (D) is heated to the specifiedprocess temperature. The Reactor Feed Furnace (9) may be a fired heaterfurnace or any other kind to type of heater as known to one of skill inthe art if it will raise the temperature of the Feedstock Mixture (D) tothe desired temperature for the process conditions.

The fully Heated Feedstock Mixture (D′) exits the Reactor Feed Furnace(9) via line 9 b and is fed into the Reactor System (11). The fullyheated Feedstock Mixture (D′) enters the Reactor System (11) whereenvironmental contaminates, such a sulfur, nitrogen, and metals arepreferentially removed from the Feedstock HMFO component of the fullyheated Feedstock Mixture. The Reactor System contains a catalyst whichpreferentially removes the sulfur compounds in the Feedstock HMFOcomponent by reacting them with hydrogen in the Activating Gas to formhydrogen sulfide. The Reactor System will also achieve demetallization,denitrogenation, and a certain amount of ring opening hydrogenation ofthe complex aromatics and asphaltenes, however minimal hydrocracking ofhydrocarbons should take place. The process conditions of hydrogenpartial pressure, reaction pressure, temperature and residence time asmeasured liquid hourly velocity are optimized to achieve desired finalproduct quality. A more detailed discussion of the Reactor System, thecatalyst, the process conditions, and other aspects of the process arecontained below in the “Reactor System Description.”

The Reactor System Effluent (E) exits the Reactor System (11) via line(11 a) and exchanges heat against the pressurized and partially heatsthe Feedstock HMFO (A′) in the Reactor Feed/Effluent Exchanger (7). Thepartially cooled Reactor System Effluent (E′) then flows via line (11 c)to the Hot Separator (13).

The Hot Separator (13) separates the gaseous components of the ReactorSystem Effluent (F) which are directed to line (13 a) from the liquidcomponents of the Reactor System effluent (G) which are directed to line(13 b). The gaseous components of the Reactor System effluent in line(13 a) are cooled against air in the Hot Separator Vapor Air Cooler (15)and then flow via line (15 a) to the Cold Separator (17).

The Cold Separator (17) further separates any remaining gaseouscomponents from the liquid components in the cooled gaseous componentsof the Reactor System Effluent (F′). The gaseous components from theCold Separator (F″) are directed to line (17 a) and fed onto the AmineAbsorber (21). The Cold Separator (17) also separates any remaining ColdSeparator hydrocarbon liquids (H) in line (17 b) from any Cold Separatorcondensed liquid water (I). The Cold Separator condensed liquid water(I) is sent OSBL via line (17 c) for treatment.

The hydrocarbon liquid components of the Reactor System effluent fromthe Hot Separator (G) in line (13 b) and the Cold Separator hydrocarbonliquids (H) in line (17 b) are combined and are fed to the Oil ProductStripper System (19). The Oil Product Stripper System (19) removes anyresidual hydrogen and hydrogen sulfide from the Product HMFO (B) whichis discharged in line (19 b) to storage OSBL. We also assume a seconddraw (not shown) may be included to withdraw a distillate product,preferably a middle to heavy distillate. The vent stream (M) from theOil Product Stripper in line (19 a) may be sent to the fuel gas systemor to the flare system that are OSBL. A more detailed discussion of theOil Product Stripper System is contained in the “Oil Product StripperSystem Description.”

The gaseous components from the Cold Separator (F″) in line (17 a)contain a mixture of hydrogen, hydrogen sulfide and light hydrocarbons(mostly methane and ethane). This vapor stream (17 a) feeds an AmineAbsorber System (21) where it is contacted against Lean Amine (J)provided OSBL via line (21 a) to the Amine Absorber System (21) toremove hydrogen sulfide from the gases making up the Activating Gasrecycle stream (C′).

Rich amine (K) which has absorbed hydrogen sulfide exits the bottom ofthe Amine Absorber System (21) and is sent OSBL via line (21 b) foramine regeneration and sulfur recovery.

The Amine Absorber System overhead vapor in line (21 c) is preferablyrecycled to the process as a Recycle Activating Gas (C′) via the RecycleCompressor (23) and line (23 a) where it is mixed with the MakeupActivating Gas (C″) provided OSBL by line (23 b). This mixture ofRecycle Activating Gas (C′) and Makeup Activating Gas (C″) to form theActivating Gas (C) utilized in the process via line (23 c) as notedabove. A Scrubbed Purge Gas stream (H) is taken from the Amine AbsorberSystem overhead vapor line (21 c) and sent via line (21 d) to OSBL toprevent the buildup of light hydrocarbons or other non-condensablehydrocarbons. A more detailed discussion of the Amine Absorber System iscontained in the “Amine Absorber System Description.”

Reactor System Description: The core process Reactor System (11)illustrated in FIG. 2 comprises a single reactor vessel loaded with theprocess catalyst and sufficient controls, valves and sensors as one ofskill in the art would readily appreciate. One of skill in the art willappreciate that the reactor vessel itself must be engineered towithstand the pressures, temperatures and other conditions (i.e.presence of hydrogen and hydrogen sulfide) of the process. Using specialalloys of stainless steel and other materials typical of such a unit arewithin the skill of one in the art and well known. As illustrated, fixedbed reactors are preferred as these are easier to operate and maintain,however other reactor types are also within the scope of the invention.

A description of the process catalyst, the selection of the processcatalyst and the loading and grading of the catalyst within the reactorvessel is contained in the “Catalyst in Reactor System”.

Alternative configurations for the core process Reactor System (11) arecontemplated. In one illustrative configuration, more than one reactorvessel may be utilized in parallel as shown in FIG. 4 to replace thecore process Reactor System (11) illustrated in FIG. 2 .

In the embodiment in FIG. 4 , each reactor vessel is loaded with processcatalyst in a similar manner and each reactor vessel in the ReactorSystem is provided the heated Feed Mixture (D′) via a common line 9 b.The effluent from each reactor vessel in the Reactor System isrecombined and forms a combined Reactor Effluent (E) for furtherprocessing as described above via line 11 a. The illustrated arrangementwill allow the three reactors to carry out the process effectivelymultiplying the hydraulic capacity of the overall Reactor System.Control valves and isolation valves may also prevent feed from enteringone reactor vessel but not another reactor vessel. In this way onereactor can be by-passed and placed off-line for maintenance andreloading of catalyst while the remaining reactors continues to receiveheated Feedstock Mixture (D′). It will be appreciated by one of skill inthe art this arrangement of reactor vessels in parallel is not limitedin number to three, but multiple additional reactor vessels can be addedas shown by dashed line reactor. The only limitation to the number ofparallel reactor vessels is plot spacing and the ability to provideheated Feedstock Mixture (D′) to each active reactor.

A cascading series in FIG. 5 can also be substituted for the singlereactor vessel Reactor System 11 in FIG. 2 . The cascading reactorvessels are loaded with process catalyst with the same or differentactivities toward metals, sulfur or other environmental contaminates tobe removed. For example, one reactor may be loaded with a highly activedemetallization catalyst, a second subsequent or downstream reactor maybe loaded with a balanced demetallization/desulfurizing catalyst, andreactor downstream from the second reactor may be loaded with a highlyactive desulfurization catalyst. This allows for greater control andbalance in process conditions (temperature, pressure, space flowvelocity, etc. . . . ) so it is tailored for each catalyst. In this wayone can optimize the parameters in each reactor depending upon thematerial being fed to that specific reactor/catalyst combination andminimize the hydrocracking reactions.

An alternative implementation of the parallel reactor concept isillustrated in greater detail in FIG. 5 . Heated Feed Mixture (D′) isprovided to the reactor System via line 9 b and is distributed amongstmultiple reactor vessels (11, 12 a, 12 b, 12 c and 12 d). Flow of heatedFeedstock to each reactor vessel is controlled by reactor inlet valves(60, 60 a, 60 b, 60 c, and 60 d) associated with each reactor vesselrespectively. Reactor Effluent (E) from each reactor vessel iscontrolled by a reactor outlet valve (62, 62 a, 62 b, 62 c and 62 d)respectively. Line 9 b has multiple inflow diversion control valves (68,68 a, 68 b and 68 c), the function and role of which will be describedbelow. Line 11 a connects the outlet of each reactor, and like Line 9 bhas multiple outflow diversion control valves (70, 70 a, 70 b and 70 c)the function and role of which will be described below. Also shown is aby-pass line defined by lower by-pass control valve (64 64 a, 64 b, 64c) and upper by-pass control valve (66, 66 a, 66 b and 66 c), betweenline 9 b and line 11 a the function and purpose of which will bedescribed below. One of skill in the art will appreciate that controlover the multiple valves and flow can be achieved using a computerizedcontrol system/distributed control system (DCS) or programmable logiccontrollers (PLC) programed to work with automatic motorized valvecontrols, position sensors, flow meters, thermocouples, etc. . . . Thesesystems are commercially available from vendors such as HoneywellInternational, Schneider Electric; and ABB. Such control systems willinclude lock-outs and other process safety control systems to preventopening of valves in manner either not productive or unsafe.

One of skill in the art upon careful review of the illustratedconfiguration will appreciate that multiple flow schemes andconfigurations can be achieved with the illustrated arrangement ofreactor vessels, control valves and interconnected lines forming thereactor System. For example, in one configuration one can: open all ofinflow diversion control valves (68, 68 a, 68 b and 68 c); open thereactor inlet valves (60, 60 a, 60 b, 60 c, and 60 d); open the reactoroutlet valves 62, 62 a, 62 b, 62 c and 62 d; open the outflow diversioncontrol valves (70, 70 a, 70 b and 70 c); and close lower by-passcontrol valve (64 64 a, 64 b, 64 c) and upper by-pass control valve (66,66 a, 66 b and 66 c), to substantially achieve a reactor configurationof five parallel reactors each receiving heated Feed Mixture (D′) fromline 9 b and discharging Reactor Effluent (E) into line 11 a. In such aconfiguration, the reactors are loaded with catalyst in substantiallythe same manner. One of skill in the art will also appreciate thatclosing of an individual reactor inlet valve and corresponding reactoroutlet valve (for example closing reactor inlet vale 60 and closingreactor outlet valve 62) effectively isolates the reactor vessel 11.This will allow for the isolated reactor vessel 11 to be brought offline and serviced and or reloaded with catalyst while the remainingreactors continue to transform Feedstock HMFO into Product HMFO.

A second illustrative configuration of the control valves allows for thereactors to work in series as shown in FIG. 4 by using the by-passlines. In such an illustrative embodiment, inflow diversion controlvalve 68 is closed and reactor inlet valve 60 is open. Reactor 11 isloaded with demetallization catalyst and the effluent from the reactorexits via open outlet control valve 62. Closing outflow diversioncontrol valve 70, the opening of lower by-pass control valve 64 andupper by-pass control valve 66, the opening of reactor inlet valve 60 aand closing of inflow diversion control valve 68 a re-routes theeffluent from reactor 11 to become the feed for reactor 12 a. reactor 12a may be loaded with additional demetallization catalyst, or atransition catalyst loading or a desulfurization catalyst loading. Oneof skill in the art will quickly realize and appreciate thisconfiguration can be extended to the other reactors 12 b, 12 c and 12 dallowing for a wide range of flow configurations and flow patternsthrough the Reactor Section. As noted, an advantage of this illustrativeembodiment of the Reactor Section is that it allows for any one reactorto be taken off-line, serviced and brought back on line withoutdisrupting the transformation of Feedstock HMFO to Product HMFO. It willalso allow a plant to adjust the configuration so that as thecomposition of the feedstock HMFO changes, the reactor configuration(number of stages) and catalyst types can be adjusted. For example ahigh metal containing Feedstock HMFO, such as a Ural residual basedHMFO, may require two or three reactors (i.e. reactors 11, 12 a and 12b) loaded with demetallization catalyst and working in series whilereactor 12 c is loaded with transition catalyst and reactor 12 d isloaded with desulfurization catalyst. Many permutations and variationscan be achieved by opening and closing control valves as needed andadjusting the catalyst loadings in each of the reactor vessels by one ofskill in the art and only for brevity need not be described. One ofskill in the art will appreciate that control over the multiple valvesand flow can be achieved using a computerized control system/distributedcontrol system (DCS) or programmable logic controllers (PLC) programedto work with automatic motorized valve controls, position sensors, flowmeters, thermocouples, etc. . . . . These systems are commerciallyavailable from vendors such as Honeywell International, SchneiderElectric; and ABB. Such control systems will include lock-outs and otherprocess safety control systems to prevent opening of valves in mannereither not productive or unsafe.

Another illustrative embodiment of the replacement of the single reactorvessel Reactor System 11 in FIG. 2 is a matrix of reactors composed ofinterconnected reactors in parallel and in series. A simple 2×2 matrixarrangement of reactors with associated control valves and piping isshown in FIG. 6 , however a wide variety of matrix configurations suchas 2×3; 3×3, etc. . . . are contemplated and within the scope of thepresent invention. As depicted in FIG. 6 , a 2 reactor by 2 reactor(2×2) matrix of comprises four reactor vessels (11, 12 a, 14 and 14 b)each with reactor inlet control valves (60, 60 a, 76, and 76 a) andreactor outlet control valves (62, 62 a, 78 and 78 a) associated witheach vessel. Horizontal flow control valves (68, 68 a, 70, 70 a, 70 b,74, 74 a, 74 b, 80, 80 a, and 80 b) regulate the flow across the matrixfrom heated Feedstock (D′) in line 9 b to discharging Reactor Effluent(E) into line 11 a. Vertical flow control valves (64, 64 a, 66, 66 a,72, 72 a, 72 b, 72 c, 82, 82 a, 84, and 84 b) control the flow throughthe matrix from line 9 b to line 11 a. One of skill in the art willappreciate that control over the multiple valves and flow can beachieved using a computerized control system/distributed control system(DCS) or programmable logic controllers (PLC) programed to work withautomatic motorized valve controls, position sensors, flow meters,thermocouples, etc. . . . . These systems are commercially availablefrom vendors such as Honeywell International, Schneider Electric; andABB. Such control systems will include lock-outs and other processsafety control systems to prevent opening of valves in manner either notproductive or unsafe.

One of skill in the art will quickly realize and appreciate that byopening and closing the valves and varying the catalyst loads present ineach reactor, many configurations may be achieved. One suchconfiguration would be to open valves numbered: 60, 62, 72, 76, 78, 80,82, 84, 72 a, 64, 66, 68 a, 60 a, 62 a, 72 b, 76 a, 78 a, and 80 b, withall other valves closed so the flow for heated Feed Mixture (D′) willpass through reactors 11, 14, 12 a and 14 a in series. Another suchconfiguration would be to open valves numbered: 60, 62, 70, 64, 66, 68a, 60 a, 62 a, 72 b, 76 a, 78 a, and 80 b, with all other valves closedso the flow of heated Feed Mixture (D′) will pass through reactors 11,12 a and 14 a (but not 14). As with the prior example, the nature of theFeedstock HSFO and the catalyst loaded in each reactor may be optimizedand adjusted to achieve the desired Product HSFO properties, however forbrevity of disclose all such variations will be apparent to one of skillin the art.

One benefit of having a multi-reactor Reactor System is that it allowsfor a reactor experiencing decreased activity or plugging because ofcoke formation can be isolated and taken off line for turn-around (i.e.deactivated, catalyst and internals replaced, etc. . . . ) without theentire plant having to shut down. Another benefit as noted above is thatit allows one to vary the catalyst loading in the Reactor System so theoverall process can be optimized for a specific Feedstock HSFO. Afurther benefit is that one can design the piping, pumps, heaters/heatexchangers, etc. . . . to have excess capacity so that when an increasein capacity is desired, additional reactors can be quickly broughton-line. Conversely, it allows an operator to take capacity off line, orturn down a plant output without having a concern about turn down andminimum flow through a reactor. While the above matrix Reactor System isdescribed referring to a fixed bed or packed bed trickle flow reactor,one of skill in the art will appreciate that other reactor types may beutilized. For example, one or more reactors may be configured to beebullated bed up flow reactors or three phase upflow bubble reactors, orcounter-current reactors, or reactive distillation reactors theconfiguration of which will be known to one of skill in the art. It isanticipated that many other operational and logistical benefits will berealized by one of skill in the art from the Reactor Systemsconfigurations disclosed.

Modular Reactor The Reactor System may be field constructed ormodularized. A significant advantage of a modularized Reactor Systemwill be the ability to change-out entire reactor vessels; as opposed tochanging out or revamping the internals of a conventional fixed in placereactor. When the active reactor must be shut down for servicing (i.e.change catalyst, replace internals, etc. . . . ); the entire reactor(reactor vessel and internal components) may be changed out at ratherthan conventionally changing out catalyst beds and internals on-site.Changing out of the reactor vessels will dramatically decrease timeplant down time by eliminating the on-site process of catalystunloading, loading and conditioning, minimize field construction/changeout activities, reduce safety risks and improve Plant operatingefficiency.

As shown in FIG. 7 , a modular Reactor System as contemplated by thepresent invention may comprise a continuous tubular reactor vessel 102defined by an outer wall surrounding an internal space. One or moreinlet flanges 104 and one or more outlet flanges 106 flange are in fluidcommunication with each other via the interior to the reactor vessel.

The outer wall of the reactor vessel is sized so it will be containedwithin a standard ISO 20 ft container (i.e. 2.43 m×2.59 m×6.06 m) or astandard ISO 40 ft container (i.e. 2.43 m×2.59 m×12.2 m) frameworkstructure 108. The outer wall of the reactor vessel will be supportedand braced within the ISO container framework in a conventional mannerknown to one of skill in that art, but not shown in the drawing so theframework and reactor vessel can be lifted and transported via truck orheavy cargo vehicles. The one or more flanged inlets and outlets aresized and positioned to accommodate the corresponding feedstockprovision piping and product outlet piping of the Plant. One or both ofthe reactor vessel head pieces can be flanged and removable using asuitably sized head flange 110. A removable reactor vessel head piecemay be desirable because it may facilitate the loading and unloading ofthe internal structures, including but not limited to trays, perforatedsupport plates, catalyst beds, structured catalyst beds, Raschig rings,Dixon rings, targeted absorbant materials such as sulfur absorbants ormetal absorbants, and combinations of these, at a location away from theactive plant (i.e. in a warehouse or other controlled environment).Modular Reactor Systems such as the one described above within an ISO 40ft. container frame have been modeled in the process to have a nameplate capacity between 1600 bpd and 2400 bpd of HSFO. When utilized incombinations together in a matrix of reactors (as disclosed herein)expansion of capacity become simply a matter of having pre-designed thesupporting utilities (i.e. piping, pumps, controls, etc. to accommodatethe addition of new reactors to the Plant. For example, a set of threerectors set in series, the first reactor containing HDM catalystloading, the second reactor containing HDT catalyst loading and thethird reactor containing HDS catalyst loading, is expected to have anoverall throughput of approximately 2000 bpd. Doubling the capacity ofthe plant can be achieved by adding a second series of three reactors.In this way additional capacity can be quickly brought on-line or takeoff-line as needed.

To change out reactor vessels, the plant should be designed with acompliant safety zone around each modular reactor, so the plant cancontinue operations while the modular Reactor System to be replaced isbrought out of service and replaced with a second Modular ReactorSystem. Within the processes of the present invention, the modularReactor System to be changed out will be hydrocarbon freed, placed undernitrogen and passivated. Passivation may be by conventional means or itmay be with a material that will harden at ambient conditions to allowfor safely disconnecting and removal of the reactor vessel. A modularReactor System filled with preconditioned catalyst will replace theremoved reactor and conditioned and brought back on-line. Reactor vesselinternals, decommissioned catalyst and the like in the replaced modularReactor System can then be unloaded and recycled off-site or at alocation more suitable for such activities. Replacement internals,thermal couple replacement, insulation material patching or replacementand other services can be performed, and catalyst materials can beloaded in the revamped modular Reactor System, under controlledconditions of temperature and humidity (and if necessary under nitrogenor other inert atmosphere) into the modular Reactor System prior totransport back to the Plant site. The refurbished modular Reactor Systemmay be filled with a material that will harden at ambient conditions andmelt when heated to secure and protect the catalyst and vessel internalsduring transportation, which is described below in greater detail. Theencapsulation/solidification of the reactor internals will allow themodular Reactor System to be more easily transported via truck or railand lifted into position and reconnected at the plant. It will beappreciated by those skilled in the art that the flanges must be sealedoff with blind flange covers whenever the modular Reactor System istransported to and from the Plant or stored in reserve on-site. One ofskill in the art will appreciate that disconnecting, removal,replacement and reconnecting a modular Reactor System may be facilitatedby hydraulic lifts or platforms or frameworks designed to securelyreceive the modular Reactor System and then lift, reorient andappropriately align and reposition of the modular Reactor System to fitthe piping within the Plant. It is within the scope of this invention tohave a hydrotreating plant in which the primary hydrotreating reactorsare removable and replaceable with a modular Reactor System such as thatdescribed herein.

Hydrotreatment catalysts utilized in the modular Reactor Systemgenerally comprise an amorphous or crystalline oxide support such as analumina, a silica, a silica alumina, or a zeolite, on which at least oneelement from groups VIII and VI of the periodic table or a combinationof a plurality of elements from these same groups is deposited, forexample solids designated CoMo/Al₂O₃, NiMo/Al₂O₃ or NiW/Al₂O₃. They maybe sulfided in advance to endow them with catalytic performances forhydrocarbon hydroconversion reactions, and in particular hydrotreatmentsuch as hydrodesulfurization, and, demetallization) and certainhydrogenation reactions. This sulfurization step carried out prior tothe catalytic step can be carried out in two manners. In situsulfurization is characterized in that the catalyst in its oxide form isinitially charged into the hydrocarbon conversion reactor forsulfurizing. Ex situ pre-sulfurization, as described in U.S. Pat. Nos.4,719,195; 5,397,756; 7,582,587 incorporated by reference)pre-sulfurization of the catalyst is carried out in a location differentfrom the location in which the catalyst operates. One of skill in theart will appreciate that the catalyst can be pre-sulfided and passivatedex situ prior to loading into the transportable reactor, or after it hasbeen loaded to prevent self-heating which may lead to spontaneouscombustion. The processes of pre-sulfiding and passivation have beendescribed in the technical and patent literature, and are well known toone of skill in the art.

For this disclosure, the term “sulfided metal particles” refers to metaloxide particles converted to the sulfide form. Further, the term “metal(s)” includes metal oxide (s) in partially reduced form. The term“pre-sulfided catalyst (s)” refers to catalysts wherein part of themetals are in the oxide form, and part of the metals may have beenconverted to the sulfide form. Pre-sulfided catalysts typically containadditional sulfur compounds which facilitate the sulfiding of theremaining metal oxides during the startup process. The term“pre-sulfided catalyst (s)” refers to catalysts wherein the majority ofthe metal oxides have been converted to metal sulfides.

As part of the ex situ passivation and optional coating of a catalyst,the sulfided catalyst undergoes at least two treatments: controlledcontact with at least one surface active oxidizing agent (also calledthe passivation step), followed (optionally) by contact with at leastone coating agent with an initial melting point of over 100° C., whichcoats the surfaces of the catalyst (also called the coating step). Theword “coating” or “coated” does not rule out some reaction leading topassivation of the catalyst surfaces.

The passivation step involves the controlled contacting of thepre-sulfided catalyst with a surface active oxidizing agent, such asoxygen and/or an oxygen-containing hydrocarbon having at least 12 carbonatoms, for a sufficient time so a sulfurized catalyst is made lessspontaneously combustible.

When the first passivation step is a treatment in the presence of a gas(or gas stream) containing oxygen (for example deriving from dry ormoist air) which can advantageously be carried out at ambienttemperature. The reaction of oxygen adsorption onto the catalyst causesan exothermic effect preferably controlled so the temperature of theproduct remains below 50° C. One possibility is to control the partialpressures of oxygen admitted to the catalyst. Then, a preferred mannerof carrying out the invention is to initially treat the catalyst with agas at a partial pressure of less than 8 kPa of oxygen, and secondlywith a gas at a partial pressure of over 8 kPa of oxygen. It is alsopossible to carry out the oxidizing passivation process directly withone or more gas streams having a partial pressure of oxygen of over 8kPa. This first stage preferably ends when the exothermic effect has allbut disappeared (i.e. when the temperature of the solid no longerincreases or only increases slightly) or, if the operator has means forlimiting the temperature increase, the second stage of coating can thenbe started earlier.

When using an oxygen containing hydrocarbon in the first passivationstep, the contact temperature is greater than about 0° C. and typicallywill range from about 15° C. to about 350° C., preferably from about 20°C. to about 150° C. The contact temperature will vary depending on themelting point or sublimation temperature of the oxygen-containinghydrocarbon. For example, when the oxygen-containing hydrocarbon is asolid or a semi-solid such as lard, the oxygen-containing hydrocarbonprocess temperature should preferably be at least at a temperature ofthe melting point of the solid or semi-solid for a time sufficient forthe catalyst to flow freely (appear “dry” and not stick or clump). In aspecific example of lard as the oxygen-containing hydrocarbon, the lardis preferably contacted at a initial temperature of about 80° C. Theprocess temperature for contacting the oxygen-containing hydrocarbon andcatalyst can be readily determined by the melting point of the solid orsemi-solid at a given pressure environment or visually by checking ifthe oxygen-containing hydrocarbon flows. Contact times will depend ontemperature and the viscosity of the oxygen-containing hydrocarbon,higher temperatures requiring shorter times and higher viscosityrequiring longer times. Times will range from about 2 minutes to about 2hours, although longer contact times can also be used.

Preferably the oxygen-containing hydrocarbon is sufficiently flowable togive a sufficient contact with the catalyst. An oxygen-containinghydrocarbon which is liquid at the elevated temperature of contact ismore preferred for ease of handling. It is preferred that theoxygen-containing hydrocarbon is a higher hydrocarbon, i.e., one havinga carbon number greater than twelve, preferably greater than sixteen,more preferably greater than twenty. The upper carbon number of usefuloxygen-containing hydrocarbon is determined by the melting point,solidification point, or smoke point of this oxygen-containinghydrocarbon. While solid fatty oxygen-containing hydrocarbon havingcarbon numbers greater than 100 can be used, they are inconvenient sincethey must be heated to such a high temperature to be converted into aliquid, although they can be used with a solvent to put them in liquidform. Oxygen-containing hydrocarbons with carbon numbers within therange from about 12 to about 100, preferably from about 16 to about 80are found most useful.

The term “oxygen-containing hydrocarbon” refers to hydrocarbon moleculescontaining at least one oxygen atom, which includes, for example, acids,acid esters, alcohols, aldehydes, ketones and ethers. Theoxygen-containing hydrocarbon may be mixtures such as acid esters andalcohols, different acid esters and the like. The oxygen-containinghydrocarbon can be primary, secondary or tertiary. The hydrocarbonmoiety can be straight or branched chain carbon atom linkages, cyclic,acyclic or aromatic. The hydrocarbon moiety can further be saturated orunsaturated. Oxygen-containing hydrocarbons include, for example, higheralcohols having at least 12, preferably 16, more preferably 20 carbonatoms such as dodecanol, hexadecanol, farnesol, hexestrol, oleylalcohol, cetyl alcohol, hexacosanol, triacontanol, cocceryl alcohol andoctacosanol; higher ethers having at least 12, preferably 16, morepreferably 20 carbon atoms such as dicetyl ether; higher ketones havingat least 12 carbon atoms, preferably 16 carbon atoms, more preferably 20carbon atoms such as palmitone, 10-hydroxypalmitone and 3-octadecanone;higher aldehydes having at least 12 carbon atoms, preferably 16, morepreferably 20 carbon atoms such as palmitaldehyde and olealdehyde;higher acids having at least 12, preferably 16, more preferably 20carbon atoms such as saturated acids such as lauric, myristic, palmitic,stearic, and docosanoic acids for example, or unsaturated higher acidssuch as palmitoleic, oleic, linoleic, linolenic, eleostearic,ricinoleic, eicosenoic, docosenoic, eicosatetraenoic, eicosapentaenoic,decosapentaenoic and docosahexaenoic; higher acid esters having at least12, preferably 16, more preferably 20 carbon atoms including mono-, di-,tri- and poly-fatty acid esters including alkyl and aryl esters of theabove acids (e.g. benzyl oleate and butyl oleate) and esters of theabove acids with mono-glyceride, di-glycerides and triglycerides andmixtures thereof. These glyceride fatty acid esters having from 16 to100, more preferably 18 to 90, most preferably 20 to 80 carbon atoms arepreferred. Some examples of commercial glyceride fatty acid estersinclude soybean oil, linseed oil, safflower oil, corn oil, sunfloweroil, cottonseed oil, olive oil, tung oil, castor oil, rapeseed oil, talloil, peanut oil, coconut oil, palm oil, canbra oil, perilla oil, lard,tallow, marine fat or oil such as fish fat or oil (e.g. herring andsardine), vegetable residues and mixtures thereof. Some examples ofcommercial higher alcohols includes alkanol mixtures such as NEODOL™alcohols from Shell Chemical Company, including mixtures of C₉, C₁₀ andC₁₁ alkanols (NEODOL™ 91 Alcohol), mixtures of C₁₂ and C₁₃ alkanols(NEODOL™ 23 Alcohol), mixtures of C₁₂, C₁₃, C₁₄ and C₁₅ alkanols(NEODOL™ 25 Alcohol), and mixtures of C₁₄ and C₁₅ alkanols (NEODOL™ 45Alcohol); the ALFOL™ Alcohols from Vista Chemical Company, includingmixtures of C₁₀ and C₁₂ alkanols (ALFOL™ 1012 Alcohol), mixtures of C₁₂and C₁₄ alkanols (ALFOL™ 1214 Alcohol), mixtures of C₁₆ and C₁₈ alkanols(ALFOL™ 1618 Alcohol) and mixtures of C₁₆, C₁₈, and C₂₀ alkanols (ALFOL™1620 Alcohol); the EPAL® Alcohols from Ethyl Chemical Company, includingmixtures of C₁₀ and C₁₂ alkanols (EPAL™ 1012 Alcohol), mixtures of C₁₂and C₁₄ alkanols (EPAL™ 1214 Alcohol) and mixtures of C₁₄, C₁₆, and C₁₈alkanols (EPAL™ 1418 Alcohol); and the TERGITOL-™ Alcohols from UnionCarbide Corporation, including mixtures of C₁₂, C₁₃, C₁₄ and C₁₅alkanols (TERGITOL-L™ 125 Alcohols). Suitable commercially availablealkanols prepared by the reduction of naturally occurring fatty acidesters includes for example, the CO and TA products of Procter andGamble Company and the TA alcohols of Ashland Oil Company. Higheroligomers and polymers of polyols such as alkylene glycols are alsosuitable as higher alcohols.

The optional coating treatment will involve the treatment of thepassivated catalyst material with a long chain waxy hydrocarbon orpolymer material to further protect the sulfided catalyst fromdeactivation. The coating agent should have a melting point no less thanthe maximum ambient air temperature (i.e. greater than about 60° C.) andmore preferably will have a melting point of over 80° C. to facilitatetransportation without premature melting. Waxy hydrocarbons should besufficiently hard (or crystalline) so the coated catalyst particles canbe formed into a solid mass. However not so hard that the solid massbecomes brittle or subject to cracking during transport. Waxes made fromhigher alkanes having a C₁₅-C₂₀ chain lengths should be sufficient, withsome limited branching. Waxes made from lipids or fatty acids or primaryor secondary long chain alcohols will also be useful. Long chainalcohols may also serve as the passivating agent disclosed above.Ideally, the wax material will have a melting point above 100° C., butlower than the lowest desired operating temperatures for the process(i.e. lower than 260° C.) to facilitate removal from the catalystmaterials. Generally upon exposure of the wax materials to elevatedtemperatures and a partial pressure of hydrogen, they are thermallyhydrocracked and rapidly removed from the active sulfided catalystmaterials. In an alternative embodiment, the coating material may bepolymeric, preferably a heat sensitive polymer such thermoplasticsexamples of which include polyethylene, polypropylene or poly butylene.One of skill in the art will appreciate that the chain length andstructure (iso-tactic v. syn-tactic v atactic) nature of the polymerchain will directly affect the properties and can be adjustedsystematically to obtain the desired properties.

In one embodiment of the invention, the passivation step is completedand the catalyst will be sufficiently passivated for handling andloading of the catalyst under controlled conditions of temperature,oxygen content (i.e. under an oxygen depleted atmosphere such asnitrogen or argon) and humidity. In such instances, the passivated (butnot coated) catalyst will be loaded into the transportable reactor toform catalyst beds and/or will be loaded into the support structures ofthe pre-structured catalyst bed. This will allow the second step ofcoating to take place in the fully catalyst loaded transportable reactoritself or (with structured supports) the coating process will beperformed on the catalyst loaded structured supports outside of thetransportable reactor so they can be loaded into the transportablereactor.

Activation of the ex-situ pre-sulfided catalyst takes place in thetransportable reactor once the transportable reactor is connected to theprocess infrastructure. The activation step may involve heating thereactor first to a temperature to melt or liquify the coating materials.The heating step will be performed under inert atmosphere (such asnitrogen or argon) which might have a measurable partial pressure ofhydrogen. The heating step continues until the desired operatingconditions of temperature and pressure are reached. This may require theintroduction of a hydrocarbon (such as low sulfur diesel, marine gasoil, low sulfur residual materials in the presence of hydrogen andoptionally a hydrocarbon. This process of pre-conditioning the catalystand the transportable reactor prior to introducing Feedstock HMFOmaterial.

Structured Catalyst Bed Turning now to the structured catalyst bed,similar beds have been disclosed in the prior art in relation to manycatalyst promoted reactions. See for example U.S. Pat. Nos. 4,731,229;5,073,236; 5,266,546; 5,431,890; 5,730,843; USUS2002068026;US20020038066; US20020068026; US20030012711; US20060065578;US20070209966; US20090188837; US2010063334; US2010228063; US20110214979;US20120048778; US20150166908; US20150275105; 20160074824; 20170101592and US20170226433, the contents of which are incorporated herein byreference. However these disclosures involve the product being distilledfrom heavier bottoms or feedstock materials. For example heavy and lightnaphtha streams are desulfurized with the desired light naphtha beingthe desired product for the gasoline pool and the heavy naphtha eitherrecycled or sent to a FCC cracker for further upgrading. The process ofthe current invention utilized the distillation separation process toremove undesired by-product hydrocarbons and gases produced by thecatalytic reaction (i.e. ammonia and hydrogen sulfide) and the desiredproduct is the bottoms stream that is catalytically treated, but notdistilled. The structured catalyst beds as described above balance thecatalyst density load, the catalyst activity load and the desired liquidspace velocity through the reactor so an effective separation ordistillation of purified lighter products can be produced. In contrastthe present process functionally combines the functioning of a reactorwith a stripper column or knock down drum. A further problem solved bythe structured catalyst bed is to reduce the pressure drop through thecatalyst beds and provision of sufficient contact of the FeedstockMixture with the catalyst and mixing with the Activating Gas.

A first illustrative embodiment of the structured catalyst beds is shownin FIG. 8 and FIG. 9 in a side view. As illustrated in FIG. 8 is acatalyst retention composed of a pair of fluid permeable corrugatedmetal sheets (202 and 204), wherein the pair of the fluid permeablecorrugated metal sheets are aligned so the corrugations are sinusoidal,have the same wave length and amplitude, but are out of phase anddefining a catalyst rich space (206) and a catalyst lean space (208).The catalyst rich space will be loaded with one or more catalystmaterials and optionally inert packing materials. The catalyst leanspace (208) may be left empty or it may be loaded with inert packingsuch as ceramic beads, inactive (non-metal containing) catalyst support,glass beads, rings, wire or plastic balls and the like. These inertpacking materials may serve the role of assisting in the mixing of theActivating Gas with the Feedstock HMFO, facilitate the removal orseparation of gaseous by products (i.e. hydrogen sulfide or ammonia)from the process mixture or facilitate the separation of any hydrocarbonby-products.

FIG. 9 shows in side perspective a plurality of catalyst retentionstructures (210, 212 and 214) formed into a structured catalyst bed(216). Structural supports (218) may be optionally incorporated into thestructured catalyst bed to lend rigidity as needed. As shown thecatalyst rich spaces are radially aligned so the catalyst rich spaces ofone catalyst retention structure is aligned with the catalyst richstructure of the adjacent layers. In the illustrated configuration, theradial angle between adjacent layers is 0° (or 180°). One of skill inthe art will appreciate that the angle of radial alignment betweenadjacent layers may be varied from 0° to 180°, preferably between 200and 1600 and more preferably 900 so the catalyst rich areas in one layerare perpendicular to the adjacent layers. It will be further appreciatedthat the alignment of a particular set of three or more layers need notbe the same. A first layer may be aligned along and define the 0° axisrelative to the other two layers; a second adjacent layer may beradially aligned along a 45° angle relative to the first layer; and thethird layer aligned along a 90° angle relative to the first layer. Thispattern of alignment may be continued until the desired number of layersis achieved. It also should be appreciated that it may be desirable toangle of the catalyst rich spaces (ie. the plane of the catalystretention structure), relative to the flow of Feedstock HMFO andActivating Gas within the reaction vessel. This relative angle isreferred to herein as the inclination angle. As shown in FIG. 9 , theinclination angel is perpendicular (90°) to the flow of Feedstock HMFOand Activating Gas through the reactor vessel. However, it will beappreciated that the inclination level may be varied between 0°, inwhich case the catalyst rich spaces are vertically aligned with the sidewalls of the reactor vessel and 90° in which case the catalyst richspaces are perpendicular to the side walls of the reactor vessel. Byvarying both the radial alignment and the inclination angle of thecatalyst rich spaces, one will be able to achieve a wide variety and beable to optimize the flow of Feedstock HMFO though the reactor vesselwith minimal plugging/coking.

A second illustrative embodiment of the structured catalyst beds isshown in FIG. 10 and FIG. 11 in a side view. As illustrated in FIG. 10 ,catalyst retention structure (300) comprises a flat fluid permeablemetal sheet (302) and a corrugated fluid permeable metal sheet (304)aligned to be co-planar and defining a catalyst rich space (306) and acatalyst lean space (308). As with the prior illustrative embodiment,the catalyst rich space will contain one or more catalyst materials andoptionally inert packing materials and the catalyst leans pace will beempty or optionally contain inert packing materials. FIG. 11 shows inside perspective a plurality of catalyst retention structures (310, 312and 314) formed into a structured catalyst bed (316). Structuralsupports (318) may be optionally incorporated into the structuredcatalyst bed to lend rigidity as needed. As shown the catalyst richspaces are radially aligned so the catalyst rich spaces of one catalystretention structure is perpendicular with the catalyst rich structure ofthe adjacent layers. In the illustrated configuration, the radial anglebetween adjacent layers is 90°. The same considerations of radialalignment and inclination of the catalyst retention structures describedabove will apply to this embodiment. The principle benefit of theillustrated structured catalyst bed is that the manufacturing processbecause affixing the flat fluid permeable sheet and the corrugated fluidpermeable sheet will be greatly simplified. Further as illustrated, ifthe corrugated sheet is constructed using 900 angle corrugations, eachcatalyst retention structure can withstand much greater weight loadingsthan if the corrugations are sinusoidal.

The loading of the catalyst structures will depend upon the particlesize of the catalyst materials and the activity level of the catalyst.The structures should be loaded so the open space will be at least 10volume % of the overall structural volume, and preferably will be up toabout 65% of the overall structural volume. Active catalyst materialsshould be loaded in the catalyst support structure at a level dependentupon the catalyst activity level and the desired level of treatment. Forexample a catalyst material highly active for desulfurization may beloaded at a lower density than a less active desulfurization catalystmaterial and yet still achieve the same overall balance of catalystactivity per volume. One of skill in the art will appreciate that bysystematically varying the catalyst loaded per volume and the catalystactivity level one may optimize the activity level and fluidpermeability levels of the structured catalyst bed. In one such example,the catalyst density is so over 50% of the open space in the catalystrich space, which may occupy only have of the over space within thestructured catalyst bed. In another example catalyst rich space is fullyloaded (i.e. dense packed into each catalyst rich space), however thecatalyst rich space may occupy only 30 volume % of the overallstructured catalyst bed. It will be appreciated that the catalystdensity in the catalyst rich space may vary between 30 vol % and 100 vol% of the catalyst rich space. It will be further appreciated that thatcatalyst rich space may occupy as little as 10 vol % of the overallstructured catalyst bed or it may occupy as much as 80 vol % of theoverall structured catalyst bed.

The liquid hourly space velocity within the structured catalyst bedsshould be between 0.05 oil/hour/m³ catalyst and 10.0 oil/hour/m³catalyst; preferably between 0.08 oil/hour/m³ catalyst and 5.0oil/hour/m³ catalyst and more preferably between 0.1 oil/hour/m³catalyst and 3.0 oil/hour/m³ catalyst to achieve deep desulfurizationusing a highly active desulfurization catalyst and this will achieve aproduct with sulfur levels below 0.1 ppmw. However, it will beappreciated by one of skill in the art that when there is lower catalystdensity, it may be desirable to adjust the space velocity to valueoutside of the values disclosed.

One of skill in the art will appreciate that the above describedstructured catalyst beds can serve as a direct substitute for densepacked beds that include inert materials, such as glass beads and thelike. An important criteria is the catalyst density within the bedsthemselves. The structured catalyst beds can be loaded with a catalystdensity comparable to that of a dense loaded bed with a mixture ofcatalyst and inert materials or a bed with layers of catalyst and inertmaterials. Determining the optimized catalyst density will be a simplematter of systematically adjusting the catalyst density (for a set ofreaction conditions in a pilot plant. A fixed density catalyst structurewill be made and the reaction parameters of space velocity and reactortemperature and bed depth will be systematically varied and optimized.

Reactive Distillation Reactor As in FIG. 12 , a reactive Reactor Systemas contemplated by the present invention will comprise a reactor vessel(400) within which one or more structured beds are provided (402, 404and 406). One of skill in the art will note that heated FeedstockMixture (D′) enters the reactor vessel in the upper portion of thereactor via line (9 b) above the structured catalyst beds (402, 404 and406). When elements are the same as those disclosed, the same referencenumber is utilized for continuity within the disclosure. Entry of theheated Feedstock Mixture (D′) above the structured catalyst beds (402,404 and 406) may be facilitated by a distribution tray or similar devicenot shown. It will also be noted that each of the structured catalystbeds is different in appears, the reason for this will now described.The upper most structured catalyst bed (402) will be preferably loadedwith a demetallization catalyst and in a structure optimized for thedemetallization of the Feedstock mixture. The middle structured catalystbed (404) will preferably be loaded with a transition catalyst materialor a mixture of demetallization and low activity desulfurizationcatalyst. The lower most structured catalyst bed will be preferablyloaded with a desulfurization catalyst of moderate to high activity. Agas sparger or separation tray (408) is below structured catalyst tray406. In this way, the Feedstock Mixture flows from the upper portion ofthe reactor to the lower portion of the reactor and will be transformedinto Reaction Mixture (E) which exits the bottom of the reactor via line11 a.

As shown, make up Activating Gas C′″ will be provided via line 414 toboth quench and create within the reactor a counter-current flow ofActivating gas within the reactor. One of skill in the art willappreciate this flow may also be connected to the reactor so make upActivating gas is also injected between structured catalyst beds 406 and404 and 404 and 402. In the upper portion of the reactor, inertdistillation packing beds (410 and 412) may be located. It may bedesirably and optionally it is preferable for the lower most of theseupper beds (410) to be a structured catalyst bed as well with catalystfor the desulfurization of the distillate materials. In such an instancea down comber tray or similar liquid diversion tray (414) is inserted soa flow of middle to heavy distillate (G′) can be removed from the upperportion of the reactor via line (426). Light hydrocarbons (i.e. lighterthan middle distillate exits the top of the reactor via line (416) andpasses through heat exchanger (7) to help with heat recovery. Thisstream is then directed to the reflux drum (418) in which liquids arecollected for use as reflux materials. The reflux loop to the upperreactor is completed via reflux pump (422) and reflux line (424). Thatportion of the lights not utilized in the reflux are combined withsimilar flows (F and G) via lines 13 a and 13 b respectively.

One of skill in the art of reactor design will note that unlike theprior art reactive distillation processes and reactor designs, thepresent invention presents multiple novel and non-obvious (i.e.inventive step) features. One such aspect, as noted above, the FeedstockMixture enters the upper portion of the reactor above the structuredcatalytic beds. In doing so it is transformed into Reaction Mixture thatexits the bottom of the reactor. One of skill in the art will appreciatethat by this flow, the majority of HMFO material (which is characterizedas being residual in nature) will not be volatile or distilled, but anybyproduct gases, distillate hydrocarbons or light hydrocarbons arevolatilized into the upper portion of the reactor. The reactor will behydraulically designed so the majority of the volume of the liquidcomponents having residual properties in the Feedstock Mixture will exitthe lower portion of the reactor, preferably over 75% vol. of the volumeof the liquid components having residual properties in the FeedstockMixture will exit the lower portion of the reactor and even morepreferably over 90% vol. of the volume of the liquid components havingresidual properties in the Feedstock Mixture will exit the lower portionof the reactor. This is in contract with the prior art where themajority of the desired products exit the upper portion of the reactorvia distillation and the residual bottoms portions are recycled or sentto another refinery unit for further processing.

In a variation of the above illustrative embodiment, one or more fixedbed reactor(s) containing, solid particle filtering media such asinactive catalyst support, inert packing materials, selective absorptionmaterials such as sulfur absorption media, demetallization catalyst orcombinations and mixtures of these may be located upstream of theReactive distillation reactor. In one alternative embodiment a reactorwith a mixture of hydrodemetallization catalyst, decarbonizationcatalysts and inert materials will act as a guard bed, protecting theReactive distillation reactor from high levels of metals, concarbon(CCR) and other contaminants that can reduce the run length of theReactive distillation reactor. In another embodiment, the upstreamreactors are loaded within inert packing materials and deactivatedcatalyst to remove solids followed by a reactor loaded withinhydrodemetallization catalyst. One of skill in the art will appreciatethese upstream reactors may allow the upstream reactors to be taken outof service and catalysts changed out without shutting down or affectingoperation of the Reactive distillation reactor.

In another variation of the above illustrative embodiment in FIG. 12 , afired reboiler can be added to the lower portion of the reactivedistillation reactor. Such a configuration would take a portion of theReaction Mixture from the bottom of the reactor prior to its exit vialine 11 a, pass it through a pump and optionally a heater, andreintroduce the material into the reactor above tray 408 and preferablyabove the lowermost structured catalyst bed (406). The purpose of thereboiler will be to add or remove heat within the reactive distillationreactor, and will increase column traffic, because of this reboiler loopa temperature profile in the reactive distillation reactor will becontrolled and more distillate product(s) may be taken. We assumeseverity in the column could be increased to increase the hydrocrackingactivity within the reactive distillation reactor increasing thedistillate production. Because of the washing effect caused by refluxingReaction Mixture back into the reactive distillation reactor, coking andfouling of catalysts should be minimized, allowing for extending runlengths.

Bubble Reactor: FIG. 13 shows a packed bubble reactor configuration asan alternative embodiment for the primary reactor. Bubble reactors arecharacterized by having a high heat and mass transfer rates, compactnessand low operating and maintenance costs. As illustrated in FIG. 13 , thereactor (502) will contain a packed catalyst bed (504) of heterogenoustransition metal catalyst materials. The packed bed may be a partiallyexpanded bed or more preferably a structured bed in which the activecatalyst material are dispersed by inert packing (glass beads) or metalstructures such as those described in U.S. and co-pending patentapplications. Catalyst supporting structures (506 and 508) may behelpful in ensuring that the catalyst materials remain in the desiredlocations within the reactor. The illustrative packed bubble reactorwill have a con-current configuration with Feedstock HSFO (510) beingintroduced into the reactor at a point below the catalyst bed.Activating Gas (512) will be so bubble are formed in the Feedstock HSFO,preferably using spargers or gas diffusion devices (514) know to one ofskill in the art. Treated HSFO (516) exits the reactor at a point abovethe catalyst bed. Unreacted Activating Gas and by-product gases, such ashydrogen sulfide and light hydrocarbons (C8 and lower) (518), exit thetop of the reactor. The inflow of Feedstock HSFO and the outflow oftreated HSFO will be managed so the fluid level (520) is maintained sothat and initial hot separation of treated HSFO and gases takes place inthe top of the reactor.

One of skill in the art will appreciate that the pack bubble reactordescribed above can also be configured to have a counter-currentconfiguration. In such an illustrative embodiment, the Activating Gas(512) will be injected at the bottom of the reactor and the unreactedActivating Gas and by-product gases, such as hydrogen sulfide and lighthydrocarbons (C8 and lower) (518), will exit the top of the reactor.However, the flow of Feedstock HSFO and treated HSFO are reversed fromthat shown in FIG. 13 so Feedstock HSFO is introduced into the top ofthe reactor (the reverse of 516) and treated HSFO is removed from thebottom of the reactor (the reverse of 510). In such a counter currentconfiguration, there is a natural grading of reaction activity from top(lowest activity based on hydrogen partial pressure in the ActivatingGas) to the bottom (greatest activity based on hydrogen partial pressurein the Activating Gas). It is expected that such a configuration will befurther optimized by the gradation of the activity levels of thecatalyst materials and will achieve significantly longer run timeswithout the formation of coke or other solids deactivating the catalystor restricting the flow of HSFO through the reactor. One of skill in theart will appreciate that by using reactor models and CFD calculations,the flows of Feedstock HSFO and Activating Gas for any catalystarrangement (packed bed, structured bed or expanded bed) can beoptimized to achieve maximum throughput and treatment of the HSFO.

Divided Wall Reactor: In a further alternative embodiment, a dividedwall reactor configuration may be desired, especially when heatpreservation is desired, such as when feed heater capabilities arelimited.

Referring now to FIG. 14 , there is illustrated a reactor system 600comprising an upper reactor section 602, first lower reactor section 604and second lower reactor section 606. The reactor system contains alongitudinally oriented partition 608 which extends through at least apart of the length of the reactor system 602 to define the partitionedfirst lower reactor section 604 and the second lower reactor section606.

Feedstock HMFO is provided into upper portion of the first reactorsection 604 through conduit means 610. Top vapor from the first reactorsection comprising gases and light and middle distillate hydrocarbons iswithdrawn from the upper portion of the first lower reactor section 602.Middle distillate hydrocarbons are condensed in the upper portion of thereactor system 602 and removed via line 611 as medium to heavydistillate (i.e. diesel and gas oil) for use and processing outside thebattery limits shown. A portion of the middle distillate hydrocarbonscan be diverted and used as a reflux (not shown) if desired, the volumeof that reflux may be minimal. The gases and light hydrocarbons collectat the top of the reactor system and exit the reactor system via line612 for later treatment. As illustrated the later treatment may comprisea heat exchanger 614 followed by a separator drum 616. The condensedhydrocarbon liquids can be used in part as a reflux to the reactorsection via pump 618 and line 620. Or in addition, the hydrocarbonliquids can be withdrawn via line 621 and processed using conventionaltechniques outside of the battery limits shown. The bottoms portion ofthe first lower reactor section 604, comprising partially treatedFeedstock HMFO is routed back into the lower section of the firstreactor section 604 to serve as a reflux via reflux loop 622.

The cross-hatched areas represent mass transfer elements such as densepacked transition metal catalyst beds (with or without inert materialssuch as glass beads); loose catalyst supported on trays, or packing. Thepacking, if used, may be structured catalyst beds or random packingcatalyst beds with inert materials mixed with the transitions metalcatalyst materials.

The partition may be made of any suitable material if there issubstantially no mass transfer across the partition, however there maybe heat transfer across the partition. The column cross-sectional areaneed not be divided equally by the partition. The partition can have anysuitable shape such as a vertical dividing plate or an internalcylindrical shell configuration. In the embodiment illustrated in FIG.14 the partition is a vertical dividing plate bisecting the reactor,however, more than one plate may form radially arranged reactorsections.

The partially treated HMFO fluid from the lower portion of the firstlower reaction section 604 is pumped through conduit means 624 into thesecond lower reaction section 606 at a point above the partitionedsection. Top vapor from the second reactor section comprising gases andlight and middle distillate hydrocarbons are withdrawn from the upperportion of the second lower reactor section 604. Middle distillatehydrocarbons are condensed in the upper portion of the reactor system602 and removed via line 611 as medium and heavy distillate hydrocarbons(i.e. diesel and gas oil) for use and processing outside the batterylimits shown. A bottoms portion of the second lower reactor section,comprising treated HMFO may be routed through recycle loop 626 back intothe lower section of the second lower reactor section 606 to serve as areflux. A second portion of the bottoms portion from the second lowerreactor section 606 is removed through line 628 for further treatmentoutside of the battery limits as treated HMFO. It may desirable forthere to be injection of make up or quenching Activating Gas in to thelower portions of the reactor. This may be achieved using Activating Gasfeedlines 630 a and 630 b. One of skill in the art will appreciate thatthe properties of the Feedstock HMFO sent to the first reactor sectionand the partially treated HMFO may be substantively the same (except forthe levels of environmental contaminates such as sulfur).

At the design stage, different packing or combinations of trays,structured catalyst beds, and packing can be specified on each side ofthe partition to alter the fraction of the HMFO which flows on each sideof the partition. Other products such as middle and heavy distillatehydrocarbons may be taken from the upper portion of the reactor system602 preferably from above the partitioned section.

In one embodiment the dividing partition is extended to the bottom ofthe part of the divided column containing trays or packing, and thesection of trays or packing above the partition is eliminated. Such anarrangement allows easy control of the reflux liquid on each side of thedivided column with a control valve (not shown) external to the column.In the embodiments illustrated in FIG. 14 flow through the lines iscontrolled in part by appropriate valving as is well known to thoseskilled in the art and these valves are not illustrated in the drawings.

One of skill in the art will appreciate the thermal benefits to bederived from the above illustrative embodiment. This benefit may be bestrealized in a modular reactor configuration or niche refiningenvironment where footprint of the unit is more important than maximumthroughput. For example, one can utilize the above arrangement to moreefficiently process relatively small volume (i.e. 500-5000 Bbl) ofFeedstock high sulfur HMFO that a refinery would otherwise have toclear/dispose of. The divided wall reactor allows for a single reactorvessel to function s two separate vessels and take advantage of thecombined collection of the by-product gases and light hydrocarbons.

While the above described reactor types may be preferred, other reactorsmay also be utilized in implementing the disclosed process. Examples ofsuch reactors are now provided in brief and without illustration as theyare described and known in the art of reactor design.

Liquid Full Reactor: Liquid full reactors such as those disclosed inU.S. Pat. Nos. 6,123,835, 6,428,686, 6,881,326, 7,291,257, 7,569,136;8,721,871; 9,365,782; US20120103868; U.S. Pat. Nos. 8,314,276; 8,008,534and also semi-liquid full reactors such as those disclosed inUS20170037325 and US20180072957 (the contents incorporated herein byreference) may be used for the removal of environmental contaminatesfrom Feedstock high sulfur HMFO having bulk properties compliant withISO 8217 (2017) except for the sulfur levels which may be in the rangeof 1-3% wt sulfur. A diluent material is disclosed as a necessaryaddition to the feedstock hydrocarbons in the above noted patents,however as contemplated in the present disclosure, using diluent orrecycling of product back into the feedstock is not required. This isbelieved to result from using a Feedstock high sulfur HMFO with bulkproperties that are ISO 817 compliant. A process is contemplated inwhich: a) contacting the Feedstock high sulfur HMFO, wherein the bulkproperties of the Feedstock high sulfur HMFO is ISO 8217 (2017)compliant except for a sulfur content which may be in the range of 0.5%wt and 5.0 wt, preferably between the range of 1.0% wt and 3.5% wtsulfur with Activating Gas so the Activating Gas saturates the Feedstockhigh sulfur HMFO; b) introducing the Activating Gas saturated Feedstockhigh sulfur HMFO into a liquid full reactor containing a transitionmetal catalyst so reactive contact occurs and a treated HMFO is formed;and c) discharging the treated HMFO from the reactor. Upon discharge,the treated HMFO can be passed through an inert gas stripper to removethe entrained gases, including light hydrocarbons and hydrogen sulfideformed in the reactor. The treated HMFO can be subjected to a second orlater treatment process substantially similar to that described. (thatis saturation of the treated HMFO with Activating Gas; contacting theActivating gas saturated treated HMFO with a transitional metal catalystto further reactive contact occurs and discharging from the reactor. Weassume under these conditions, multiple reactors may be desirable isstages to achieve the desired degree of desulfurization (i.e. less than0.5% wt and more preferably less than 0.1% wt sulfur). In such aninstance, a first reactor stage is loaded with a transition metalcatalyst characterized as a hydrodemetallization catalyst; a secondreactor stage is loaded with a transition metal catalyst characterizedas a transition catalyst (which is a graded mixture ofhydrodemetallization catalyst and hydrodesulfurization catalyst so thereis an increase in desulfurization activity further downstream); and athird reactor stage is loaded with a transition metal catalystcharacterized as a hydrodesulfurization catalyst. Each stage may involvemore than one actual reactor vessels. For example, the first stage(demetallization) can comprise two reactors with catalyst loaded sothere is an increasing level of demetallization activity furtherdownstream; followed by the transition catalyst stage and then followedby the desulfurization stage. Or for a sulfur rich feedstock, there canbe multiple reactors making up the third desulfurization stage. Theconcept of having three reactor stages (demetallization, transition,desulfurization) made up of one or more reactors is not limited toliquid full reactors, but can be implemented in the other reactorsdisclosed.

Ebulliated Bed or Slurry Bed Reactors Ebulliated bed or slurry bedreactors such as those disclosed in U.S. Pat. Nos. 7,390,393; 6,712,955;6,132,597; 6,153,087; 6,187,174; 6,207,041; 6,277,270; 3,623,974;4,285,804; 3,657,111; 3,619,410; 3,617,503; 3,079,329; 4,125,455;4,902,407; 4,746,419; 4,576,710; 4,591,426; 3,809,644; 3,705,849; (thecontents incorporated herein by reference) may be used for the removalof environmental contaminates from Feedstock high sulfur HMFO havingbulk properties compliant with ISO 8217 (2017) except for the sulfurlevels which may be in the range of 1-3% wt sulfur. A Co-catalyst in theform of particulate transition metal compounds is disclosed as anecessary addition to the feedstock hydrocarbons in certain of the abovenoted slurry bed patents, this diluent may take the form of a lighterthan Feedstock HSFO material (i.e. middle distillate or gas oil) orrecycling of portion of the by product back into the feedstock. Aprocess is contemplated in which: a) contacting the Feedstock highsulfur HMFO, wherein the bulk properties of the Feedstock high sulfurHMFO is ISO 8217 (2017) compliant except for a sulfur content which maybe in the range of 0.5% wt and 5.0 wt, preferably between the range of1.0% wt and 3.5% wt sulfur with Activating Gas in the reactor so theActivating Gas saturates the Feedstock high sulfur HMFO; b) introducingthe Activating Gas saturated Feedstock high sulfur HMFO into aebulliated bed reactor containing a transition metal catalyst soreactive contact occurs and a treated HMFO is formed; and c) dischargingthe treated HMFO from the reactor. Upon discharge, the treated HMFO canbe passed through an inert gas stripper to remove the entrained gases,including light hydrocarbons and hydrogen sulfide formed in the reactor.The treated HMFO can be subjected to a second or later treatment processsubstantially similar to that described. (that is saturation of thetreated HMFO with Activating Gas; contacting the Activating gassaturated treated HMFO with a transitional metal catalyst to furtherreactive contact occurs and discharging from the reactor. We assumeunder these conditions, multiple reactors may be desirable is stages toachieve the desired degree of desulfurization (i.e. less than 0.5% wtand more preferably less than 0.1% wt sulfur). In such an instance, afirst reactor stage is loaded with a transition metal catalystcharacterized as a hydrodemetallization catalyst; a second reactor stageis loaded with a transition metal catalyst characterized as a transitioncatalyst (which is a graded mixture of hydrodemetallization catalyst andhydrodesulfurization catalyst so there is an increase in desulfurizationactivity further downstream); and a third reactor stage is loaded with atransition metal catalyst characterized as a hydrodesulfurizationcatalyst. Each stage may involve more than one actual reactor vessels.For example, the first stage (demetallization) can comprise two reactorswith catalyst loaded so there is an increasing level of demetallizationactivity further downstream; followed by the transition catalyst stageand then followed by the desulfurization stage. Or for a sulfur richfeedstock, there can be multiple reactors making up the thirddesulfurization stage

Catalyst in Reactor System: The reactor vessel in each Reactor System isloaded with one or more process catalysts. The exact design of theprocess catalyst system is a function of feedstock properties, productrequirements and operating constraints and optimization of the processcatalyst can be carried out by routine trial and error by one ofordinary skill in the art.

The process catalyst(s) comprise at least one metal selected from thegroup consisting of the metals each belonging to the groups 6, 8, 9 and10 of the Periodic Table, and more preferably a mixed transition metalcatalyst such as Ni—Mo, Co—Mo, Ni—W or Ni—Co—Mo are utilized. The metalis preferably supported on a porous inorganic oxide catalyst carrier.The porous inorganic oxide catalyst carrier is at least one carrierselected from the group consisting of alumina, alumina/boria carrier, acarrier containing metal-containing aluminosilicate, alumina/phosphoruscarrier, alumina/alkaline earth metal compound carrier, alumina/titaniacarrier and alumina/zirconia carrier. The preferred porous inorganicoxide catalyst carrier is alumina. The pore size and metal loadings onthe carrier may be systematically varied and tested with the desiredfeedstock and process conditions to optimize the properties of theProduct HMFO. One of skill in the art knows that demetallization using atransition metal catalyst (such a CoMo or NiMo) is favored by catalystswith a relatively large surface pore diameter and desulfurization isfavored by supports having a relatively small pore diameter. Generallythe surface area for the catalyst material ranges from 200-300 m²/g. Thesystematic adjustment of pore size and surface area, and transitionmetal loadings activities to preferentially form a demetallizationcatalyst or a desulfurization catalyst are well known and routine to oneof skill in the art. Catalyst in the fixed bed reactor(s) may bedense-loaded or sock-loaded and including inert materials (such as glassor ceric balls) may be needed to ensure the desired porosity.

The catalyst selection utilized within and for loading the ReactorSystem may be preferential to desulfurization by designing a catalystloading scheme that results in the Feedstock mixture first contacting acatalyst bed that with a catalyst preferential to demetallizationfollowed downstream by a bed of catalyst with mixed activity fordemetallization and desulfurization followed downstream by a catalystbed with high desulfurization activity. In effect the first bed withhigh demetallization activity acts as a guard bed for thedesulfurization bed.

The objective of the Reactor System is to treat the Feedstock HMFO atthe severity required to meet the Product HMFO specification.Demetallization, denitrogenation and hydrocarbon hydrogenation reactionsmay also occur to some extent when the process conditions are optimizedso the performance of the Reactor System achieves the required level ofdesulfurization. Hydrocracking is preferably minimized to reduce thevolume of hydrocarbons formed as by-product hydrocarbons to the process.The objective of the process is to selectively remove the environmentalcontaminates from Feedstock HMFO and minimize the formation ofunnecessary by-product hydrocarbons (C1-C8 hydrocarbons).

The process conditions in each reactor vessel will depend upon thefeedstock, the catalyst utilized and the desired properties of theProduct HMFO. Variations in conditions are to be expected by one ofordinary skill in the art and these may be determined by pilot planttesting and systematic optimization of the process. With this in mind ithas been found that the operating pressure, the indicated operatingtemperature, the ratio of the Activating Gas to Feedstock HMFO, thepartial pressure of hydrogen in the Activating Gas and the spacevelocity all are important parameters to consider. The operatingpressure of the Reactor System should be in the range of 250 psig and3000 psig, preferably between 1000 psig and 2500 psig and morepreferably between 1500 psig and 2200 psig. The indicated operatingtemperature of the Reactor System should be 500° F. to 900° F.,preferably between 650° F. and 850° F. and more preferably between 680°F. and 800° F. The ratio of the quantity of the Activating Gas to thequantity of Feedstock HMFO should be in the range of 250 scf gas/bbl ofFeedstock HMFO to 10,000 scf gas/bbl of Feedstock HMFO, preferablybetween 2000 scf gas/bbl of Feedstock HMFO to 5000 scf gas/bbl ofFeedstock HMFO and more preferably between 2500 scf gas/bbl of FeedstockHMFO to 4500 scf gas/bbl of Feedstock HMFO. The Activating Gas should beselected from mixtures of nitrogen, hydrogen, carbon dioxide, gaseouswater, and methane, so Activating Gas has an ideal gas partial pressureof hydrogen (p_(H2)) greater than 80% of the total pressure of theActivating Gas mixture (P) and preferably wherein the Activating Gas hasan ideal gas partial pressure of hydrogen (p_(H2)) greater than 90% ofthe total pressure of the Activating Gas mixture (P). The Activating Gasmay have a hydrogen mole fraction in the range between 80% of the totalmoles of Activating Gas mixture and more preferably wherein theActivating Gas has a hydrogen mole fraction between 80% and 90% of thetotal moles of Activating Gas mixture. The liquid hourly space velocitywithin the Reactor System should be between 0.05 oil/hour/m³ catalystand 1.0 oil/hour/m³ catalyst; preferably between 0.08 oil/hour/m³catalyst and 0.5 oil/hour/m³ catalyst and more preferably between 0.1oil/hour/m³ catalyst and 0.3 oil/hour/m³ catalyst to achieve deepdesulfurization with product sulfur levels below 0.1 ppmw.

The hydraulic capacity rate of the Reactor System should be between 100bbl of Feedstock HMFO/day and 100,000 bbl of Feedstock HMFO/day,preferably between 1000 bbl of Feedstock HMFO/day and 60,000 bbl ofFeedstock HMFO/day, more preferably between 5,000 bbl of FeedstockHMFO/day and 45,000 bbl of Feedstock HMFO/day, and even more preferablybetween 10,000 bbl of Feedstock HMFO/day and 30,000 bbl of FeedstockHMFO/day. The desired hydraulic capacity may be achieved in a singlereactor vessel Reactor System or in a multiple reactor vessel ReactorSystem as described.

Oil Product Stripper System Description: The Oil Product Stripper System(19) comprises a stripper column (also known as a distillation column orexchange column) and ancillary equipment including internal elements andutilities required to remove hydrogen, hydrogen sulfide and hydrocarbonslighter than diesel from the Product HMFO. Such systems are well knownto one of skill in the art, see U.S. Pat. Nos. 6,640,161; 5,709,780;5,755,933; 4,186,159; 3,314,879 U.S. Pat. Nos. 3,844,898; 4,681,661; orU.S. Pat. No. 3,619,377 the contents of which are incorporated herein byreference, a generalized functional description is provided herein.Liquid from the Hot Separator (13) and Cold Separator (7) feed the OilProduct Stripper Column (19). Stripping of hydrogen and hydrogen sulfideand hydrocarbons lighter than diesel may be achieved via a reboiler,live steam or other stripping medium. The Oil Product Stripper System(19) may be designed with an overhead system comprising an overheadcondenser, reflux drum and reflux pump or it may be designed without anoverhead system. The conditions of the Oil Product Stripper may beoptimized to control the bulk properties of the Product HMFO, morespecifically viscosity and density. We also assume a second draw (notshown) may be included to withdraw a distillate product, preferably amiddle to heavy distillate.

Amine Absorber System Description: The Amine Absorber System (21)comprises a gas liquid contacting column and ancillary equipment andutilities required to remove sour gas (i.e. hydrogen sulfide) from theCold Separator vapor feed so the resulting scrubbed gas can be recycledand used as Activating Gas. Because such systems are well known to oneof skill in the art, see U.S. Pat. Nos. 4,425,317; 4,085,199; 4,080,424;4,001,386; which are incorporated herein by reference, a generalizedfunctional description is provided herein. Vapors from the ColdSeparator (17) feed the contacting column/system (19). Lean Amine (orother suitable sour gas stripping fluids or systems) provided from OSBLis utilized to scrub the Cold Separator vapor so hydrogen sulfide iseffectively removed. The Amine Absorber System (19) may be designed witha gas drying system to remove the any water vapor entrained into theRecycle Activating Gas (C′). The absorbed hydrogen sulfide is processedusing conventional means OSBL in a tail gas treating unit, such as aClaus combustion sulfur recovery unit or sulfur recovery system thatgenerates sulfuric acid.

These examples will provide one skilled in the art with a more specificillustrative embodiment for conducting the process disclosed and claimedherein:

Example 1

Overview: The purpose of a pilot test run is to demonstrate thatfeedstock HMFO can be processed through a reactor loaded withcommercially available catalysts at specified conditions to removeenvironmental contaminates, specifically sulfur and other contaminantsfrom the HMFO to produce a product HMFO that is MARPOL compliant, thatis production of a Low Sulfur Heavy Marine Fuel Oil (LS-HMFO) orUltra-Low Sulfur Heavy Marine Fuel Oil (USL-HMFO).

Pilot Unit Set Up: The pilot unit will be set up with two 434 cm³reactors arranged in series to process the feedstock HMFO. The leadreactor will be loaded with a blend of a commercially availablehydro-demetaling (HDM) catalyst and a commercially availablehydro-transition (HDT) catalyst. One of skill in the art will appreciatethat the HDT catalyst layer may be formed and optimized using a mixtureof HDM and HDS catalysts combined with an inert material to achieve thedesired intermediate/transition activity levels. The second reactor willbe loaded with a blend of the commercially available hydro-transition(HDT) and a commercially available hydrodesulfurization (HDS). One canload the second reactor simply with a commercially hydrodesulfurization(HDS) catalyst. One of skill in the art will appreciate that thespecific feed properties of the Feedstock HMFO may affect the proportionof HDM, HDT and HDS catalysts in the reactor system. A systematicprocess of testing different combinations with the same feed will yieldthe optimized catalyst combination for any feedstock and reactionconditions. For this example, the first reactor will be loaded with ⅔hydro-demetaling catalyst and ⅓ hydro-transition catalyst. The secondreactor will be loaded with all hydrodesulfurization catalyst. Thecatalysts in each reactor will be mixed with glass beads (approximately50% by volume) to improve liquid distribution and better control reactortemperature. For this pilot test run, one should use these commerciallyavailable catalysts: HDM: Albemarle KFR 20 series or equivalent; HDT:Albemarle KFR 30 series or equivalent; HDS: Albemarle KFR 50 or KFR 70or equivalent. Once set up of the pilot unit is complete, the catalystcan be activated by sulfiding the catalyst using dimethyldisulfide(DMDS) in a manner well known to one of skill in the art.

Pilot Unit Operation: Upon completion of the activating step, the pilotunit will be ready to receive the feedstock HMFO and Activating Gasfeed. For the present example, the Activating Gas can be technical gradeor better hydrogen gas. The mixed Feedstock HMFO and Activating Gas willbe provided to the pilot plant at rates and operating conditions asspecified: Oil Feed Rate: 108.5 ml/h (space velocity=0.25/h);Hydrogen/Oil Ratio: 570 Nm3/m3 (3200 scf/bbl); Reactor Temperature: 372°C. (702° F.); Reactor Outlet Pressure: 13.8 MPa(g) (2000 psig).

One of skill in the art will know that the rates and conditions may besystematically adjusted and optimized depending upon feed properties toachieve the desired product requirements. The unit will be brought to asteady state for each condition and full samples taken so analyticaltests can be completed. Material balance for each condition should beclosed before moving to the next condition.

Expected impacts on the Feedstock HMFO properties are: Sulfur Content(wt %): Reduced by at least 80%; Metals Content (wt %): Reduced by atleast 80%; MCR/Asphaltene Content (wt %): Reduced by at least 30%;Nitrogen Content (wt %): Reduced by at least 20%; C1-Naphtha Yield (wt%): Not over 3.0% and preferably not over 1.0%.

Process conditions in the Pilot Unit can be systematically adjusted asper Table 1 to assess the impact of process conditions and optimize theperformance of the process for the specific catalyst and feedstock HMFOutilized.

TABLE 1 Optimization of Process Conditions HC Feed Rate Pressure (ml/h),Nm³ H₂/m³ oil/ Temp (MPa(g)/ Case [LHSV(/h)] scf H₂/bbl oil (° C./° F.)psig) Baseline 108.5 [0.25] 570/3200 372/702 13.8/2000 T1 108.5 [0.25]570/3200 362/684 13.8/2000 T2 108.5 [0.25] 570/3200 382/720 13.8/2000 L1130.2 [0.30] 570/3200 372/702 13.8/2000 L2 86.8 [0.20] 570/3200 372/70213.8/2000 H1 108.5 [0.25] 500/2810 372/702 13.8/2000 H2 108.5 [0.25]640/3590 372/702 13.8/2000 S1 65.1 [0.15] 620/3480 385/725 15.2/2200

In this way, the conditions of the pilot unit can be optimized toachieve less than 0.5% wt. sulfur product HMFO and preferably a 0.1% wt.sulfur product HMFO. Conditions for producing ULS-HMFO (i.e. 0.1% wt.sulfur product HMFO) will be: Feedstock HMFO Feed Rate: 65.1 ml/h (spacevelocity=0.15/h); Hydrogen/Oil Ratio: 620 Nm³/m³ (3480 scf/bbl); ReactorTemperature: 385° C. (725° F.); Reactor Outlet Pressure: 15 MPa(g) (2200psig)

Table 2 summarizes the anticipated impacts on key properties of HMFO.

TABLE 2 Expected Impact of Process on Key Properties of HMFO PropertyMinimum Typical Maximum Sulfur Conversion/Removal 80% 90% 98% MetalsConversion/Removal 80% 90% 100%  MCR Reduction 30% 50% 70% AsphalteneReduction 30% 50% 70% Nitrogen Conversion 10% 30% 70% C1 through NaphthaYield 0.5%  1.0%  4.0%  Hydrogen Consumption (scf/bbl) 500 750 1500

Table 3 lists analytical tests to be carried out for thecharacterization of the Feedstock HMFO and Product HMFO. The analyticaltests include those required by ISO for the Feedstock HMFO and theproduct HMFO to qualify and trade in commerce as ISO compliant residualmarine fuels. The additional parameters are provided so that one skilledin the art can understand and appreciate the effectiveness of theinventive process.

TABLE 3 Analytical Tests and Testing Procedures Sulfur Content ISO 8754or ISO 14596 or ASTM D4294 Density @ 15° C. ISO 3675 or ISO 12185Kinematic Viscosity @ 50° C. ISO 3104 Pour Point, ° C. ISO 3016 FlashPoint, ° C. ISO 2719 CCAI ISO 8217, ANNEX B Ash Content ISO 6245 TotalSediment - Aged ISO 10307-2 Micro Carbon Residue, mass % ISO 10370 H2S,mg/kg IP 570 Acid Number ASTM D664 Water ISO 3733 Specific ContaminantsIP 501 or IP 470 (unless indicated otherwise) Vanadium or ISO 14597Sodium Aluminum or ISO 10478 Silicon or ISO 10478 Calcium or IP 500 Zincor IP 500 Phosphorous IP 500 Nickle Iron Distillation ASTM D7169 C:HRatio ASTM D3178 SARA Analysis ASTM D2007 Asphaltenes, wt % ASTM D6560Total Nitrogen ASTM D5762 Vent Gas Component Analysis FID GasChromatography or comparable

Table 4 contains the Feedstock HMFO analytical test results and theProduct HMFO analytical test results expected from the inventive processthat indicate the production of a LS HMFO. It will be noted by one ofskill in the art that under the conditions, the levels of hydrocarboncracking will be minimized to levels substantially lower than 10%, morepreferably less than 5% and even more preferably less than 1% of thetotal mass balance.

TABLE 4 Analytical Results Feedstock Product HMFO HMFO Sulfur Content,mass % 3.0   0.3 Density @ 15° C., kg/m³ 990 950 ⁽¹⁾ Kinematic Viscosity@ 50° C., mm²/s 380 100 ⁽¹⁾ Pour Point, ° C. 20 10  Flash Point, ° C.110 100 ⁽¹⁾ CCAI 850 820  Ash Content, mass % 0.1   0.0 Total Sediment -Aged, mass % 0.1   0.0 Micro Carbon Residue, mass % 13.0   6.5 H2S,mg/kg 0 0 Acid Number, mg KO/g 1   0.5 Water, vol % 0.5 0 SpecificContaminants, mg/kg Vanadium 180 20  Sodium 30 1 Aluminum 10 1 Silicon30 3 Calcium 15 1 Zinc 7 1 Phosphorous 2 0 Nickle 40 5 Iron 20 2Distillation, ° C./° F. IBP 160/320 120/248  5% wt 235/455 225/437 10%wt 290/554 270/518 30% wt 410/770 370/698 50% wt  540/1004 470/878 70%wt  650/1202  580/1076 90% wt  735/1355  660/1220 FBP  820/1508 730/1346 C:H Ratio (ASTM D3178) 1.2   1.3 SARA Analysis Saturates 1622  Aromatics 50 50  Resins 28 25  Asphaltenes 6 3 Asphaltenes, wt % 6.0  2.5 Total Nitrogen, mg/kg 4000 3000   Note: ⁽¹⁾ property will beadjusted to a higher value by post process removal of light material viadistillation or stripping from product HMFO.

The product HMFO produced by the inventive process will reach ULS HMFOlimits (i.e. 0.1% wt. sulfur product HMFO) by systematic variation ofthe process parameters, for example by a lower space velocity or byusing a Feedstock HMFO with a lower initial sulfur content.

Example 2: RMG-380 HMFO

Pilot Unit Set Up: A pilot unit was set up as noted above in Example 1with these changes: the first reactor was loaded with: as the first(upper) layer encountered by the feedstock 70% vol Albemarle KFR 20series hydro-demetaling catalyst and 30% vol Albemarle KFR 30 serieshydro-transition catalyst as the second (lower) layer. The secondreactor was loaded with 20% Albemarle KFR 30 series hydrotransitioncatalyst as the first (upper) layer and 80% vol hydrodesulfurizationcatalyst as the second (lower) layer. The catalyst was activated bysulfiding the catalyst with dimethyldisulfide (DMDS) in a manner wellknown to one of skill in the art.

Pilot Unit Operation: Upon completion of the activating step, the pilotunit was ready to receive the feedstock HMFO and Activating Gas feed.The Activating Gas was technical grade or better hydrogen gas. TheFeedstock HMFO was a commercially available and merchantable ISO 8217(2017) compliant HMFO, except for a high sulfur content (2.9 wt %). Themixed Feedstock HMFO and Activating Gas was provided to the pilot plantat rates and conditions as specified in Table 5 below. The conditionswere varied to optimize the level of sulfur in the product HMFOmaterial.

TABLE 5 Process Conditions Product HC Feed Nm³ H₂/m³ Temp Pressure HMFORate (ml/h), oil/scf H₂/ (° C./ (MPa(g)/ Sulfur Case [LHSV(/h)] bbl oil° F.) psig) % wt. Baseline 108.5 [0.25] 570/3200 371/700 13.8/2000 0.24T1 108.5 [0.25] 570/3200 362/684 13.8/2000 0.53 T2 108.5 [0.25] 570/3200382/720 13.8/2000 0.15 L1 130.2 [0.30] 570/3200 372/702 13.8/2000 0.53S1  5.1 [0.15] 620/3480 385/725 15.2/2200 0.10 P1 108.5 [0.25] 570/3200371/700 /1700 0.56 T2/P1 108.5 [0.25] 570/3200 382/720 /1700 0.46

Analytical data for a representative sample of the feedstock HMFO andrepresentative samples of product HMFO are below:

TABLE 6 Analytical Results - HMFO (RMG-380) Feedstock Product ProductSulfur Content, mass % 2.9 0.3 0.1 Density @ 15° C., kg/m³ 988 932 927Kinematic Viscosity @ 50° C., mm²/s 382 74 47 Pour Point, ° C. −3 −12−30 Flash Point, ° C. 116 96 90 CCAI 850 812 814 Ash Content, mass %0.05 0.0 0.0 Total Sediment - Aged, mass % 0.04 0.0 0.0 Micro CarbonResidue, mass % 11.5 3.3 4.1 H2S, mg/kg 0.6 0 0 Acid Number, mg KO/g 0.30.1 >0.05 Water, vol % 0 0.0 0.0 Specific Contaminants, mg/kg Vanadium138 15 <1 Sodium 25 5 2 Aluminum 21 2 <1 Silicon 16 3 1 Calcium 6 2 <1Zinc 5 <1 <1 Phosphorous <1 2 1 Nickle 33 23 2 Iron 24 8 1 Distillation,° C./° F. IBP 178/352 168/334 161/322  5% wt 258/496 235/455 230/446 10%wt 298/569 270/518 264/507 30% wt 395/743 360/680 351/664 50% wt 517/962461/862 439/822 70% wt  633/1172  572/1062  552/1026 90% wt  >720/>1328 694/1281  679/1254 FBP  >720/>1328  >720/>1328  >720/>1328 C:H Ratio(ASTM D3178) 1.2 1.3 1.3 SARA Analysis Saturates 25.2 28.4 29.4Aromatics 50.2 61.0 62.7 Resins 18.6 6.0 5.8 Asphaltenes 6.0 4.6 2.1Asphaltenes, wt % 6.0 4.6 2.1 Total Nitrogen, mg/kg 3300 1700 1600

In Table 6, both feedstock HMFO and product HMFO exhibited observed bulkproperties consistent with ISO 8217 (2017) for a merchantable residualmarine fuel oil, except that the sulfur content of the product HMFO wasreduced as noted above when compared to the feedstock HMFO.

One of skill in the art will appreciate that the above product HMFOproduced by the inventive process has achieved not only an ISO 8217(2017) compliant LS HMFO (i.e. 0.5% wt. sulfur) but also an ISO 8217(2017) compliant ULS HMFO limits (i.e. 0.1% wt. sulfur) product HMFO.

Example 3: RMK-500 HMFO

The feedstock to the pilot reactor utilized in example 2 above waschanged to a commercially available and merchantable ISO 8217 (2017)RMK-500 compliant HMFO, except that it has high environmentalcontaminates (i.e. sulfur (3.3 wt %)). Other bulk characteristic of theRMK-500 feedstock high sulfur HMFO are provide below:

TABLE 7 Analytical Results- Feedstock HMFO (RMK-500) Sulfur Content,mass % 3.3 Density @ 15° C., kg/m³ 1006 Kinematic Viscosity @ 50° C.,mm²/s 500

The mixed Feedstock (RMK-500) HMFO and Activating Gas was provided tothe pilot plant at rates and conditions and the resulting sulfur levelsachieved in the table below

TABLE 8 Process Conditions Product HC Feed Rate Nm³ H₂/m³ Temp Pressure(RMK-500) (ml/h), oil/scf H₂/ (° C./ (MPa(g)/ sulfur Case [LHSV(/h)] bbloil ° F.) psig % wt. A 108.5 [0.25]  640/3600 377/710 13.8/2000 0.57 B95.5 [0.22] 640/3600 390/735 13.8/2000 0.41 C 95.5 [0.22] 640/3600390/735 11.7/1700 0.44 D 95.5 [0.22] 640/3600 393/740 10.3/1500 0.61 E95.5 [0.22] 640/3600 393/740 17.2/2500 0.37 F 95.5 [0.22] 640/3600393/740  8.3/1200 0.70 G 95.5 [0.22] 640/3600 416/780  8.3/1200

The resulting product (RMK-500) HMFO exhibited observed bulk propertiesconsistent with the feedstock (RMK-500) HMFO, except that the sulfurcontent was reduced as noted in the above table.

One of skill in the art will appreciate that the above product HMFOproduced by the inventive process has achieved a LS HMFO (i.e. 0.5% wt.sulfur) product HMFO having bulk characteristics of a ISO 8217 (2017)compliant RMK-500 residual fuel oil. It will also be appreciated thatthe process can be successfully carried out under non-hydrocrackingconditions (i.e. lower temperature and pressure) that substantiallyreduce the hydrocracking of the feedstock material. When conditions wereincreased to much higher pressure (Example E) a product with a lowersulfur content was achieved, however some observed that there was anincrease in light hydrocarbons and wild naphtha production.

It will be appreciated by those skilled in the art that changes could bemade to the illustrative embodiments described above without departingfrom the broad inventive concepts thereof. It is understood, therefore,that the inventive concepts disclosed are not limited to theillustrative embodiments or examples disclosed, but it should covermodifications within the scope of the inventive concepts as defined bythe claims.

1. A process for the production of a Product Heavy Marine Fuel Oil, theprocess comprising: a. mixing a quantity of a Heavy Marine Fuel Oil witha quantity of an Activating Gas to give a Feedstock Mixture, i. whereinimmediately prior to said mixing said Heavy Marine Fuel Oil is compliantwith ISO 8217 (2017) as a Table 2 residual marine fuel, except saidHeavy Marine Fuel Oil has one or more Environmental Contaminantsselected from the group consisting of: sulfur; vanadium, nickel, iron,aluminum and silicon and combinations thereof, ii. and wherein said oneor more Environmental Contaminants have a combined concentration greaterthan 0.5% wt.; b. providing said Feedstock Mixture to a Reaction System,i. wherein the Reaction System is comprised of one or more reactorvessels, and wherein each of the one or more reactor vessels containsone or more reaction sections configured and subject to reactiveconditions for catalytic hydrogenation of the Feedstock Mixture to aProcess Mixture, and ii. wherein the catalytic hydrogenation utilizes aprocess catalyst comprising at least one metal selected from the groupconsisting of the metals each belonging to the groups 6, 8, 9 and 10 ofthe Periodic Table supported on a porous inorganic oxide catalystcarrier; and thereby, c. forming a Process Mixture from said FeedstockMixture, i. wherein said Process Mixture comprises a Product HeavyMarine Fuel Oil component; d. receiving by fluid communication saidProcess Mixture in at least one separation vessel; e. separating theProduct Heavy Marine Fuel Oil component from said Process Mixture insaid at least one separation vessel; and, f. discharging said ProductHeavy Marine Fuel Oil component from said at least one separation vesselforming the Product Heavy Marine Fuel Oil.
 2. The process of claim 1,wherein the process catalyst is comprises a mixed transition metalcatalyst wherein the mixed transition metal catalyst is selected fromthe group consisting of Ni—Mo, Co—Mo, Ni—W or Ni—Co—Mo, and wherein theporous inorganic oxide catalyst carrier is at least one carrier selectedfrom the group consisting of alumina, alumina/boria carrier, a carriercontaining metal-containing aluminosilicate, alumina/phosphorus carrier,alumina/alkaline earth metal compound carrier, alumina/titania carrierand alumina/zirconia carrier.
 3. The process of claim 2 wherein thesurface area for the process catalyst ranges from 200-300 m²/g.
 4. Theprocess of claim 1, wherein the Reaction System is comprised of sixreactor vessels, configured to form a first reactor train comprisingthree reactor vessels arranged sequentially and a second reactor traincomprising three reactor vessels arranged sequentially, and wherein thefirst reactor train is arranged in parallel to the second reactor train,and wherein the process further comprises the step of distributing ofthe Feedstock Mixture is selected from the group of steps consisting of:distributing substantially all of the Feedstock Mixture to the firstreactor train and passing the Feedstock Mixture through the firstreactor train forming the Process Mixture; distributing substantiallyall of the Feedstock Mixture to the second reactor train and passing theFeedstock Mixture through the second reactor train forming the ProcessMixture; and distributing a first portion of the Feedstock Mixture tothe first reactor train and passing the first portion of the FeedstockMixture through the first reactor train, and distributing a secondportion of the Feedstock Mixture to the second reactor train and passingthe second portion of the Feedstock Mixture through the second reactortrain and then subsequently combining the first portion from the firstreactor train and the second portion of from the second reactor train,and passing the combined first and second portions to and receiving byfluid communication said combined first and second portions ProcessMixture in at least one separation vessel and separating the one or morebulk gaseous components of said Process Mixture from a combined one ormore liquid hydrocarbon components, and one or more residual gaseouscomponents entrained in said hydrocarbon liquid components.
 5. Theprocess of claim 4, wherein the first reactor vessel and second reactorvessel in each of the first reactor train and second reactor train isloaded with a first catalyst system wherein the first catalyst system isindependently selected from the group consisting of: ahydrodemetallization catalyst material; a hydrotransition catalystmaterial; an inert catalyst material; and, combinations thereof, andwherein the third reactor in each of the first reactor train and secondreactor train is loaded with a second catalyst system, wherein thesecond catalyst system is independently selected from the groupconsisting of: a hydrotransition catalyst material, ahydrodesulfurization catalyst material; an inert catalyst material; and,combinations thereof.
 6. The process of claim 1 wherein said ProductHeavy Marine Fuel Oil discharged by the process complies with ISO 8217(2017) as a Table 2 residual marine fuel, and said Product Heavy MarineFuel Oil has one or more Environmental Contaminants with a combinedconcentration between the range of 0.50 mass % to 0.05 mass %.
 7. Theprocess of claim 1 wherein said Product Heavy Marine Fuel Oil dischargedfrom the process complies with ISO 8217 (2017) as a Table 2 residualmarine fuel and one of the one or more Environmental Contaminants issulfur and the sulfur content of the Product Heavy Marine Fuel Oil isbetween the range of 0.50 mass % to 0.05 mass %.
 8. The process of claim1 wherein the reactive conditions comprise: the ratio of the quantity ofthe Activating Gas to the quantity of Heavy Marine Fuel Oil is in therange of 250 scf gas/bbl of Heavy Marine Fuel Oil to 10,000 scf gas/bblof Heavy Marine Fuel Oil; a total pressure is between of 250 psig and3000 psig; and, the indicated temperature is between of 500° F. to 900°F., and, wherein the liquid hourly space velocity is between 0.05 h⁻¹and 1.0 h⁻¹.
 9. A process for the removal of one or more EnvironmentalContaminants from a Heavy Marine Fuel Oil, the process comprising: a.mixing a quantity of said Heavy Marine Fuel Oil with a quantity ofActivating Gas to give a Feedstock Mixture, i. wherein prior to mixingwith Activating Gas, said Heavy Marine Fuel Oil complies with ISO 8217(2017) as a Table 2 residual marine fuel except said Heavy Marine FuelOil has one or more Environmental Contaminants selected from the groupconsisting of: sulfur; vanadium, nickel, iron, aluminum and silicon andcombinations thereof, and wherein said one or more EnvironmentalContaminants have a combined concentration greater than 0.5% wt., andii. wherein said Activating Gas has an ideal gas partial pressure ofhydrogen (p_(H2)) greater than 80% of the total pressure of theActivating Gas (P); b. providing by fluid communication the FeedstockMixture in a Reaction System, i. wherein the Reaction System iscomprised of one or more reactor vessels, and
 1. wherein each of the oneor more reactor vessels contains one or more fixed catalyst bedsconfigured and subject to reactive conditions for the catalytichydroprocessing of the Feedstock Mixture to a Process Mixture and 2.wherein the fixed catalyst bed is dense-loaded or sock loaded withcatalyst materials comprising at least one metal selected from the groupconsisting of the metals each belonging to the groups 6, 8, 9 and 10 ofthe Periodic Table supported on a porous inorganic oxide catalystcarrier, and ii. wherein the Feedstock Mixture is passed through atleast one catalyst bed under reactive conditions of hydrodemetallizationor hydrodesulfurization or both; and thereby, c. forming a ProcessMixture from said Feedstock Mixture, i. wherein said Process Mixturecomprises a Product Heavy Marine Fuel Oil component; d. receiving byfluid communication said Process Mixture in at least one separationvessel; e. separating the Product Heavy Marine Fuel Oil component fromsaid Process Mixture in said at least one separation vessel; and, f.discharging said Product Heavy Marine Fuel Oil component from said atleast one separation vessel forming the Product Heavy Marine Fuel Oil.10. The process of claim 9 wherein the catalyst materials areindependently selected from the group consisting of: ahydrodemetallization catalyst material; a hydrotransition catalystmaterial; a hydrodesulfurization catalyst material, an inert catalystmaterial; and, combinations thereof.
 11. The process of claim 9, whereinthe process catalyst is comprises a mixed transition metal catalystwherein the mixed transition metal catalyst is selected from the groupconsisting of Ni—Mo, Co—Mo, Ni—W or Ni—Co—Mo, and wherein the porousinorganic oxide catalyst carrier is at least one carrier selected fromthe group consisting of alumina, alumina/boria carrier, a carriercontaining metal-containing aluminosilicate, alumina/phosphorus carrier,alumina/alkaline earth metal compound carrier, alumina/titania carrierand alumina/zirconia carrier.
 12. The process of claim 1 wherein thesurface area for the process catalyst ranges from 200-300 m²/g.
 13. Theprocess of claim 9 wherein prior to the step of receiving by fluidcommunication said Process Mixture in at least one separation vessel andseparating the Product Heavy Marine Fuel Oil component from said ProcessMixture, the Process Mixture remains under reactive conditions in theReaction System and is distributed to and contacted with at least onesecond catalyst bed under reactive conditions, wherein the secondcatalyst bed is comprised of catalyst materials independently selectedfrom the group consisting of: a hydrotransition catalyst material, ahydrodesulfurization catalyst material; an inert catalyst material; and,combinations thereof.
 14. The process of claim 9 wherein said ProductHeavy Marine Fuel Oil complies with ISO 8217 (2017), as a Table 2residual marine fuel and said Product Heavy Marine Fuel Oil has one ormore Environmental Contaminants with a combined concentration betweenthe range of 0.50 mass % to 0.05 mass %.
 15. The process of claim 9wherein said Product Heavy Marine Fuel Oil complies with ISO 8217 (2017)as a Table 2 residual marine fuel, and one of the one or moreEnvironmental Contaminants is sulfur and the sulfur content of theProduct Heavy Marine Fuel Oil is between the range of 0.50 mass % to0.05 mass %.
 16. The process of claim 9 wherein the reactive conditionscomprise: the ratio of the quantity of the Activating Gas to thequantity of Heavy Marine Fuel Oil is in the range of 250 scf gas/bbl ofHeavy Marine Fuel Oil to 10,000 scf gas/bbl of Heavy Marine Fuel Oil; atotal pressure is between of 250 psig and 3000 psig; and, the indicatedtemperature is between of 500° F. to 900° F., and, wherein the liquidhourly space velocity is between 0.05 h⁻¹ and 1.0 h⁻¹.
 17. A modularreactor comprising: a reaction vessel having an exterior shell thatdefines an interior space; one or more inlet piping connections toprovide fluid communication between a source of feedstock and theinterior space of reaction vessel; one or more outlet piping connectionsto provide fluid communication between the interior of the reactionvessel and product removal piping; a supporting framework surroundingthe reaction vessel, the supporting frame work providing the reactionvessel with structural support, and wherein the supporting framework istransportable; and there is one or more internal structures within theinterior space of the reaction vessel, wherein the internal structuresare selected from the group consisting of: trays, perforated supportplates, catalyst beds, structured catalyst beds, Raschig rings, Dixonrings, absorbent materials and combinations of these.
 18. The modularreactor of claim 17, wherein the supporting framework has dimensions ofan ISO 40 foot container.
 19. The modular reactor of claim 17, whereinthe interior space of the reaction vessel contains a catalyst, whereinthe catalyst comprises: a porous inorganic oxide catalyst carrier and atransition metal catalyst, wherein the porous inorganic oxide catalystcarrier is at least one carrier selected from the group consisting ofalumina, alumina/boria carrier, a carrier containing metal-containingaluminosilicate, alumina/phosphorus carrier, alumina/alkaline earthmetal compound carrier, alumina/titania carrier and alumina/zirconiacarrier, and wherein the transition metal catalyst is one or more metalsselected from the group consisting of group 6, 8, 9 and 10 of thePeriodic Table.
 20. The modular reactor of claim 17, wherein thecatalyst is pre-sulfided and coated with oxygen containing hydrocarbonto passivate the catalyst and wherein the modular reactor contains asecondary protective coating agent that is a long chain waxy hydrocarbonor polymer material to protect the passivated catalyst and internalstructures of the modular reactor during transport and installation,wherein the secondary protective coating agent has a melting pointgreater than about 60° C.